Multi-layered films for use in airbags and footwear

ABSTRACT

Airsoles or bladders for articles of footwear comprising multi-layered films are provided herein. In one aspect, the airsoles or bladders comprise a first sheet and a second sheet, wherein a first side of the first sheet faces a second side of the second sheet, wherein the first sheet and the second sheet are bonded together to form an internal cavity in a space between the first side of the first sheet and the second side of the second sheet, forming a bladder capable of retaining a gas in the internal cavity at a pressure above atmospheric pressure, at atmospheric pressure, or below atmospheric pressure; and wherein each of the first sheet and the second sheet comprise a multi-layered film comprising: a core region comprising at least 20 gas barrier layers and a plurality of elastomeric layers, wherein the gas-barrier layers alternate with the elastomeric layers.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.63/203,612 filed on Jul. 27, 2021, which is incorporated herein byreference in its entirety.

TECHNICAL FIELD

The present disclosure is directed to multi-layered films. Morespecifically, the present disclosure relates to multi-layered filmshaving gas-barrier properties, methods of making such multi-layeredfilms, articles incorporating the multi-layered films (e.g., airbags,fuel hose liners, and vehicle tires), and methods for manufacturing sucharticles. The present disclosure also relates to articles of footwearthat incorporate the airbags.

BACKGROUND

This section provides background information related to the presentdisclosure which is not necessarily prior art.

The design of athletic equipment and apparel as well as footwearinvolves a variety of factors from the aesthetic aspects, to the comfortand feel, to the performance and durability. While design and fashionmay be rapidly changing, the demand for increasing performance in themarket is unchanging. To balance these demands, designers employ avariety of materials and designs for the various components that make upathletic equipment and apparel as well as footwear.

Articles of footwear conventionally include an upper and a solestructure. The upper may be formed from any suitable material(s) toreceive, secure, and support a foot on the sole structure. The upper maycooperate with laces, straps, or other fasteners to adjust the fit ofthe upper around the foot. A bottom portion of the upper, proximate to abottom surface of the foot, attaches to the sole structure.

Sole structures generally include a layered arrangement extendingbetween a ground surface and the upper. One layer of the sole structureincludes an outsole that provides abrasion-resistance and traction withthe ground surface. The outsole may be formed from rubber or othermaterials that impart durability and wear-resistance, as well as enhancetraction with the ground surface. Another layer of the sole structureincludes a midsole disposed between the outsole and the upper. Themidsole provides cushioning for the foot and may be partially formedfrom a polymer foam material that compresses resiliently under anapplied load to cushion the foot by attenuating ground-reaction forces.Sole structures may also include a comfort-enhancing insole or asockliner located within a void proximate to the bottom portion of theupper and a strobel attached to the upper and disposed between themidsole and the insole or sockliner.

BRIEF DESCRIPTION OF THE DRAWINGS

Further aspects of the present disclosure will be readily appreciatedupon review of the detailed description, described below, when taken inconjunction with the accompanying drawings.

FIG. 1 is a bottom front perspective view of an article of footwearincorporating a multi-layered film of the present disclosure.

FIG. 2 is an exploded perspective view of the article of footwear shownin FIG. 1 .

FIG. 3 is a top schematic view of the article of footwear with an upperof the footwear omitted for discussion purposes to show a footprint of amidsole chassis and airsole.

FIG. 4 is a sectional view of a multi-layered film of the presentdisclosure, such as for use in the article of footwear and the airsoleshown in FIGS. 1-3 .

FIG. 5 is an expanded sectional view of a core region of themulti-layered film of the present disclosure.

FIGS. 6A-6E are sectional views of alternative multi-layered films ofthe present disclosure.

FIGS. 7A-7B show an exemplary article of athletic equipment (i.e., asoccer ball) incorporating the multi-layered film of the presentdisclosure.

FIGS. 8A-8B show a tire incorporating the multi-layered film of thepresent disclosure.

FIGS. 9A-9C show micrographs illustrating extent of cracking in bladdersformed from various configurations of layers as disclosed herein afterbeing subjected to KIM testing as described herein.

FIG. 10A shows a comparison of gas transmission rates for a controlbladder including 32 EVOH layers (bottom curve) versus a bladder having24 EVOH layers with 50 percent thickness of the control (top curve) anda bladder having 32 EVOH layers with 50 percent thickness of the control(middle curve). FIGS. 10B-10C are micrographs showing the lack ofcracking in the 24 EVOH layer bladder and 32 EVOH layer bladder,respectively, after being subjected to KIM testing as described herein.

FIG. 11A shows a comparison of gas transmission rates (GTR) for acontrol bladder including 32 EVOH layers (bottom curve) versus a bladderhaving 24 EVOH layers with 50 percent thickness of the control (topcurve) and a bladder having 32 EVOH layers with 75 percent thickness ofthe control (middle curve). FIG. 11B is a micrograph showing mildcracking in the 32 EVOH layer bladder after being subjected to KIMtesting as described herein.

FIG. 12 shows a comparison of gas transmission rates for a controlbladder including 32 EVOH layers (curve with squares) versus a bladderhaving 64 EVOH layers with 150 percent thickness compared to the control(curve with circles) and a bladder having 40 EVOH layers withapproximately the same thickness as the control (curve with triangles).

Corresponding reference numerals indicate corresponding parts throughoutthe drawings.

DESCRIPTION

The present disclosure is directed to a multi-layered film (e.g.,microlayer film) having thin gas-barrier layers, which have been foundto increase film flexibility while also retaining good film durabilityand gas-barrier properties. As such, the multi-layered film of thepresent disclosure is suitable for use in a variety of articlesrequiring gas-barrier and/or gas-retention properties, e.g., airbags,fuel hose liners, vehicle tires, and the like. The multi-layered film isparticularly suitable for use in articles that require gas-barrierand/or gas-retention properties while also being subjected to repeatedflexing conditions, such as airbags for use in footwear cushioning(referred to as “airsoles,” as defined below).

Fluid-filled bladders, including bladders configured for use ascushioning elements, may be formed from multi-layered films that includegas-barrier layers. The gas-barrier layers may be brittle enough todevelop cracking (and/or crazing) over time. For example, this may occurafter multiple cycles of flexing and release. Cracking (and/or crazing)may become visible to the naked eye. It may reduce the transparency ofone or more areas of the cushioning element. It may increase the gastransmission rate of the cushioning element.

Bladders having bulbous protrusions and/or areas of relatively smallradii of curvature may be more likely to crack. Therefore, these typesof bladders are at particular risk of visible defects. They are also atrisk of an unacceptable increase in gas transmission rate resulting fromaligned cracks in many, even all, layers (catastrophic cracking). Therehas therefore been a general reluctance in the present field to producethese types of bladders commercially, particularly bladders which areused as cushioning elements, as they will be exposed to a very largenumber of flexing and release cycles during use.

Proposals to mitigate increased gas transmission rate due to cracking,and to reduce the visibility of cracks once they have formed, includeincreasing the thickness of individual gas-barrier layers present in thefilm; and increasing the number of gas-barrier layers present in thefilm. Either of these options may lead to an increase in the overallamount of gas-barrier material present in the multi-layered film.

In a multi-layered film having a core region including a gas-barriermaterial, the core region of the film presents the greatest barrier torapid diffusion of gas molecules. When cracks are present in thegas-barrier material forming the gas-barrier layers of the core region,a gas molecule is able to bypass the gas-barrier material, and diffusemore rapidly through the more gas-permeable materials present in thefilm. When cracks are aligned throughout many or all layers of the coreregion of a gas-barrier film, a gas molecule can pass through largeportions of the core region of the film or even through the entire coreregion of the film in a relatively short amount of time. Increasing thenumber of gas-barrier layers decreases the likelihood that cracks willoccur in an aligned manner in a large number of layers or in all layersof the core. When cracks are not aligned, a gas molecule is forced totake a tortuous path in order to pass through the overall multi-layeredfilm. A similar effect has been proposed upon increasing individualgas-barrier layer thicknesses. However, it has until now not been wellunderstood how to prevent or diminish the formation of cracks in thegas-barrier layers in the first place.

Unexpectedly, it has now been found that decreasing the thickness ofeach individual gas-barrier layer may prevent or diminish the formationof cracks in the layers. Instead of using average individual gas-barrierlayer thicknesses of several micrometers, individual average gas-barrierlayer thicknesses of less than or equal to 0.75 micrometers, (optionallyof less than or equal to 0.5 micrometers), including in a range of about0.01 micrometers to about 0.75 micrometers (optionally, in a range ofabout 0.01 micrometers to about 0.5 micrometers), are proposed. Averageindividual gas-barrier layer thicknesses of below about 0.75micrometers, and optionally of below about 0.5 micrometers, have beenfound to reduce cracking and may reduce catastrophic cracking of thetype mentioned above. It has also been found that the use of thesethinner layers in multi-layered films may result in films and bladdersthat have a gas transmission rate (that is, without taking into accountany cracks, i.e., for films or bladders prior to exposure to flexing andrelease) which remains satisfactory compared to the gas transmissionrate of thicker layers. In particular, the gas transmission rate for thefilms or bladders may be less than or equal to 4 cubic centimeters persquare meter per day, or less than or equal to 3 cubic centimeters persquare meter per day.

It has surprisingly been found that when these thinner layers are used,it is not necessary to compensate in other ways. For example, it is notnecessary to increase the overall amount of gas-barrier material, oreven to maintain the same overall amount of gas-barrier material byincreasing the number of gas-barrier layers when their individualthicknesses are reduced. This is in contrast to the proposals toincrease the number of gas-barrier layers or increase the thickness ofeach individual gas-barrier layer; both of which tend to lead to anincrease in the overall amount of gas-barrier material.

It has been found that it is possible to use a relatively low number ofgas-barrier layers, for example about 20 gas-barrier layers (forexample, about 24 gas-barrier layers, thus fewer layers than the 32gas-barrier layers of the control bladders of the Examples set outhereinbelow) although more gas-barrier layers may be used, for exampleat least 30 gas-barrier layers or at least 40 gas-barrier layers, inorder to provide particularly low gas transmission rates. The number ofgas-barrier layers may optionally be no more than 70. There may be noneed for particularly large amounts of gas-barrier material to bepresent overall in the multi-layered films.

The more crack- and craze-resistant multi-layered films disclosed hereinmay be used to make bladders (for example, cushioning elements) with awider variety of shapes and for a wider variety of uses, than haspreviously been possible. Cushioning elements having bulbous protrusionsand/or areas of relatively small radii of curvature may be made, whichmaintain high clarity and low gas diffusion rates for long periods ofuse.

As used herein, the terms “airbag” and “bladder” are interchangeable andeach refers to either a fluid-inflated and sealed component or afluid-inflatable and sealable component, the latter of which can beinflated with one or more fluids and sealed. As can be appreciated, thesealed and sealable terms can refer to fixed seals (e.g., with weldedseams) and/or to dynamic seals that can switch between open and closedstates (e.g., with valves). Furthermore, the airbags discussed hereincan each have a single interior cavity that can be inflated with afluid, multiple interior cavities that are separate and can beindependently inflated with one or more fluids, and/or multiple interiorcavities that are fluidly connected (at least some of them) and that canbe inflated with one or more fluids, and combinations thereof. Asfurther used herein, the term “airsole” refers to an airbag used ascushioning element in a footwear midsole component to provide cushioningand/or support to an article of footwear.

The shape of a bladder typically includes an upper surface and a lowersurface, with a sidewall positioned between the upper surface and thelower surface. While bladders may be shaped so that the sidewallincludes either convex or concave curved regions, it is common for thesidewalls to include convex regions which curve away from and extendbeyond the upper surface of the bladder or from the lower surface of thebladder or from both the upper surface and the lower surface of thebladder. When the bladder is a midsole component of an article offootwear, the upper surface of the bladder may be positioned so that itfaces the insole of the article of footwear or the cavity within theupper of the article of footwear configured to contain the foot of awearer during use, while the lower surface of the bladder may bepositioned so that it faces the outsole of the article of footwear orthe ground. It is common for a curved region of the sidewall to bevisible from the outer surface of the article of footwear, or even to beexposed and form a portion of the outer surface of the article offootwear. As used herein, the term “bulbous protrusion” or “bulbousportion” may refer to a portion or region of a bladder having one ormore of the following characteristics, such as at least two, at leastthree, or all four of the following characteristics. The bulbousprotrusion or bulbous portion may be a curved sidewall of the bladder,including a convexly curved sidewall of the bladder. In particular, abulbous protrusion or bulbous portion may be a part of a rearwardlyand/or laterally extending bladder in an article of footwear, whichprojects more than 1 millimeter, optionally more than 2 millimeters,optionally more than 3 mm, optionally more than 4 millimeters,optionally more than 5 millimeters, beyond the upper or lower surface ofthe bladder (alternatively, beyond the rear of the article of footwear)and/or beyond one or more sides of the article of footwear. When flexed,the bulbous protrusion or portion of the bladder may extend evenfurther, such as by more than an additional 1 millimeter, or more thanan additional 2 millimeters, or more than an additional 3 millimeters.Additionally or alternatively, the bulbous protrusion or bulbous portionmay be a concavely or convexly curved surface, particularly a convexlycured surface, having a curvature that is at least about twice, at leastabout three times, or even at least about five times, the minimumcurvature found elsewhere in the bladder. Additionally or alternatively,the bulbous protrusion or bulbous portion may be a concavely or convexlycurved surface (such as a convexly-curved sidewall of a bladder in anarticle of footwear), where the height of the curved surface (such asits height when disposed in an article of footwear) is at least about 50percent higher, at least about 100 percent higher, or at least about 150percent higher than the minimum height found elsewhere in the bladder.Additionally or alternatively, the bulbous protrusion or bulbous portionmay include a concavely or convexly curved surface, particularly aconvexly-curved sidewall, having a radius of curvature that is less thanhalf, less than a third, or even less than a fifth, of the maximumradius of curvature found elsewhere in the bladder.

The multi-layered film or multiple sheets of the multi-layered film canbe shaped into a variety of wall geometries for airbags (e.g., bythermoforming, blow molding, etc.) and the produced airbag can beinflated with one or more fluids (e.g., one or more gases) and sealedfor use in a variety of applications, notably as footwear airsoles.

Aspects

The following list of exemplary aspects supports and is supported by thedisclosure provided herein.

In accordance with aspect 1, the present disclosure is directed to amulti-layered film comprising:

one or more core regions, wherein each of the one or more core regionscomprises a plurality of layers, the plurality of layers comprisinggas-barrier layers comprising at least one gas-barrier material, thegas-barrier layers alternating with elastomeric layers comprising atleast one elastomeric material,

wherein an average thickness of each of the gas-barrier layers is in arange from about 0.5 micrometers to about 2 micrometers, optionally fromabout 0.5 micrometers to about 1 micrometer; or an average thickness ofeach of the gas-barrier layers is in a range of about 0.01 to about 0.75micrometers, optionally in a range of about 0.01 to about 0.5micrometers; and

wherein an average thickness of each of the elastomeric layers is fromabout 2 micrometers to about 8 micrometers thick, optionally from about2 micrometers to about 4 micrometers thick.

In accordance with aspect 2, the present disclosure is directed to themulti-layered film of aspect 1, wherein the number of gas-barrier layersin each of the one or more core regions is in a range of from about 20to about 70; optionally, wherein each of the one or more core regionscomprises at least about 40 layers, optionally from about 50 to about100 layers, from about 50 to about 90 layers, from about 50 to about 80layers, from about 50 to about 70 layers, from about 60 to about 100layers, from about 60 to about 90 layers, or from about 60 to about 80layers.

In accordance with aspect 3, the present disclosure is directed to themulti-layered film of aspect 1 or 2, wherein each of the one or morecore regions has an average total thickness less than 200 micrometers.

In accordance with aspect 4, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, wherein thegas-barrier material comprises a nitrogen gas-barrier material.

In accordance with aspect 5, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, wherein thegas-barrier material comprises or consists essentially of one or moregas-barrier polymers, and wherein the gas-barrier material comprises agas-barrier polymeric component consisting of all polymers present inthe gas-barrier material.

In accordance with aspect 6, the present disclosure is directed to themulti-layered film of aspect 5, wherein the one or more gas-barrierpolymers comprise or consist essentially of one or more thermoplasticvinylidene chloride polymers, one or more thermoplastic acrylonitrilepolymers or copolymers, one or more thermoplastic polyamides, one ormore thermoplastic epoxy resins, one or more thermoplastic aminepolymers or copolymers, or one or more thermoplastic polyolefinhomopolymers or copolymers.

In accordance with aspect 7, the present disclosure is directed to themulti-layered film of aspect 6, wherein the one or more thermoplasticpolyolefin homopolymers or copolymers comprise or consist essentially ofone or more thermoplastic polyethylene copolymers.

In accordance with aspect 8, the present disclosure is directed to themulti-layered film of aspect 6, wherein the one or more thermoplasticpolyolefin homopolymers or copolymers comprise or consist essentially ofone or more thermoplastic ethylene-vinyl alcohol copolymers.

In accordance with aspect 9, the present disclosure is directed to themulti-layered film of aspect 8, wherein the one or more thermoplasticethylene-vinyl alcohol copolymers include from about 28 mole percent toabout 44 mole percent ethylene content, optionally from about 32 molepercent to about 44 mole percent ethylene content.

In accordance with aspect 10, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, wherein theelastomeric material comprises or consists essentially of one or morethermoplastic elastomeric polymers, and wherein the elastomeric materialcomprises an elastomeric polymeric component consisting of all polymerspresent in the elastomeric material.

In accordance with aspect 11, the present disclosure is directed to themulti-layered film of aspect 10, wherein the one or more thermoplasticelastomeric polymers comprise or consist essentially of one or morethermoplastic elastomeric polyolefin homopolymers or copolymers, one ormore thermoplastic elastomeric polyamide homopolymers or copolymers, oneor more thermoplastic elastomeric polyester homopolymers or copolymers,one or more thermoplastic elastomeric polyurethane homopolymers orcopolymers, one or more thermoplastic elastomeric styrenic homopolymersor copolymers, or any combination thereof.

In accordance with aspect 12, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, wherein theelastomeric material comprises or consists essentially of one or morethermoplastic elastomeric polyurethane homopolymers or copolymers,optionally wherein the elastomeric material comprises or consistsessentially of one or more polydiene polyol-based thermoplasticelastomeric polyurethane homopolymers or copolymers.

In accordance with aspect 13, the present disclosure is directed to themulti-layered film of aspect 12, wherein the one or more thermoplasticelastomeric polyurethane homopolymers or copolymers comprise a pluralityof first segments derived from one or more polyols and a plurality ofsecond segments derived from a diisocyanate.

In accordance with aspect 14, the present disclosure is directed to themulti-layered film of aspect 12, wherein the one or more thermoplasticelastomeric polyurethane homopolymers or copolymers is a polymerizationproduct of a diisocyanate with one or more polyols.

In accordance with aspect 15, the present disclosure is directed to themulti-layered film of aspect 12, wherein the thermoplastic elastomericpolyurethane homopolymer or copolymer comprises or consists essentiallyof one or more polydiene polyol-based thermoplastic elastomericpolyurethane homopolymers or copolymers and wherein the polyol comprisesor consists essentially of a polybutadiene polyol, a polyisoprenepolyol, a partially or fully hydrogenated derivative of a polybutadienepolyol or of a polyisoprene polyol, or any combination thereof.

In accordance with aspect 16, the present disclosure is directed to themulti-layered film of aspect 13 or 14, wherein the one or more polyolscomprise or consist essentially of a polyester polyol, a polyetherpolyol, a polycarbonate polyol, a polycaprolactone polyether, or anycombination thereof.

In accordance with aspect 17, the present disclosure is directed to themulti-layered film of aspect 13, 14, or 16, wherein the diisocyanatecomprises or consists essentially of an aliphatic diisocyanate, anaromatic diisocyanate, or any combination thereof.

In accordance with aspect 18, the present disclosure is directed to themulti-layered film of aspect 17, wherein the aliphatic diisocyanatecomprises or consists essentially of hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), butylenediisocyanate (BDI),bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylenediisocyanate (TMDI), bisisocyanatomethylcyclohexane,bisisocyanatomethyltricyclodecane, norbornane diisocyanate (NDI),cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate(H12MDI), diisocyanatododecane, lysine diisocyanate, or any combinationthereof.

In accordance with aspect 19, the present disclosure is directed to themulti-layered film of aspect 17, wherein the aromatic diisocyanatecomprises or consists essentially of toluene diisocyanate (TDI), TDIadducts with trimethylolpropane (TMP), methylene diphenyl diisocyanate(MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate(TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate,para-phenylene diisocyanate (PPDI),3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 4,4′-dibenzyldiisocyanate (DBDI), 4-chloro-1,3-phenylene diisocyanate, or anycombination thereof.

In accordance with aspect 20, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, wherein thegas-barrier material has a melt flow index of from about 5 to about 7grams per 10 minutes at 190 degrees Celsius when using a weight of 2.16kilograms.

In accordance with aspect 21, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, wherein theelastomeric material has a melt flow index of from about 20 to about 30grams per 10 minutes at 190 degrees Celsius when using a weight of 2.16kilograms.

In accordance with aspect 22, the present disclosure is directed to themulti-layered film of aspect 20 or 21, wherein the melt flow index ofthe gas-barrier material is from about 80 percent to about 120 percentof the melt flow index of the elastomeric material, optionally fromabout 90 percent to about 110 percent of the melt flow index of theelastomeric material, from about 95 percent to about 105 percent of themelt flow index of the elastomeric material, or wherein the melt flowindex of the gas-barrier material is substantially the same as the meltflow index of the elastomeric material, wherein the melt flow index ismeasured in cubic centimeters per 10 minutes at 190 degrees Celsius whenusing a weight of 2.16 kilograms.

In accordance with aspect 23, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, wherein thegas-barrier material has a melting temperature of from about 165 degreesCelsius to about 183 degrees Celsius.

In accordance with aspect 24, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, wherein theelastomeric material has a melting temperature of from about 155 degreesCelsius to about 165 degrees Celsius.

In accordance with aspect 25, the present disclosure is directed to themulti-layered film of aspect 23 or 24, wherein the melting temperatureof the gas-barrier material is within about 10 degrees Celsius of themelting temperature of the elastomeric material, optionally within about8 degrees Celsius of the melting temperature of the elastomericmaterial, or within about 5 degrees Celsius of the melting temperatureof the elastomeric material.

In accordance with aspect 26, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, furthercomprising a blended material, wherein the blended material comprises orconsists essentially of a blend of one or more additional thermoplasticelastomers and a second material, optionally wherein the second materialcomprises or consists essentially of one or more second polymers,optionally wherein the one or more second polymers comprise or consistessentially of one or more second thermoplastics.

In accordance with aspect 27, the present disclosure is directed to themulti-layered film of aspect 26, wherein the one or more secondthermoplastics comprise one or more thermoplastic polyolefinhomopolymers or copolymers, one or more thermoplastic polyamidehomopolymers or copolymers, one or more thermoplastic polyesterhomopolymers or copolymers, one or more thermoplastic polyurethanehomopolymers or copolymers, one or more thermoplastic styrenichomopolymers or copolymers, or any combination thereof.

In accordance with aspect 28, the present disclosure is directed to themulti-layered film of aspect 26 or 27, wherein the one or more secondthermoplastics comprise or consist essentially of thermoplasticpolypropylene homopolymers or copolymers, thermoplastic polyethylenehomopolymers or copolymers, thermoplastic polybutylene homopolymers orcopolymers, or any combination thereof.

In accordance with aspect 29, the present disclosure is directed to themulti-layered film of any one of aspects 26-28, wherein the one or moresecond thermoplastics comprise or consist essentially of one or morethermoplastic polyethylene copolymers.

In accordance with aspect 30, the present disclosure is directed to themulti-layered film of any one of aspects 26-29, wherein the one or moresecond thermoplastics comprise or consist essentially of one or morethermoplastic ethylene-vinyl alcohol copolymers.

In accordance with aspect 31, the present disclosure is directed to themulti-layered film of any one of aspects 26-30, wherein a polymericcomponent of the blended material consists of one or more additionalthermoplastic elastomeric polyurethane homopolymers or copolymers, andone or more second thermoplastic ethylene-vinyl alcohol copolymers.

In accordance with aspect 32, the present disclosure is directed to themulti-layered film of any one of aspects 26-31, wherein the polymericcomponent of the thermoplastic elastomeric material consists of one ormore additional thermoplastic elastomeric polyester-polyurethanecopolymers and one or more second thermoplastic ethylene-vinyl alcoholcopolymers.

In accordance with aspect 33, the present disclosure is directed to themulti-layered film of any one of aspects 26-32, wherein the blendedmaterial comprises one or more recycled additional thermoplasticelastomers, or one or more recycled second thermoplastics, or both.

In accordance with aspect 34, the present disclosure is directed to themulti-layered film of any one of aspects 26-33, wherein the blendedmaterial is a phase-separated blend of the one or more additionalthermoplastic elastomers and the one or more second thermoplastics.

In accordance with aspect 35, the present disclosure is directed to themulti-layered film of aspect 34, wherein the phase-separated blendincludes one or more phase-separated regions including interfacesbetween the one or more additional thermoplastic elastomers and the oneor more second thermoplastics.

In accordance with aspect 36, the present disclosure is directed to themulti-layered film of any one of aspects 26-35, wherein the blendcomprises about 95 percent by weight of the one or more additionalthermoplastic elastomers and about 5 percent by weight of the one ormore second thermoplastics based on a total weight of the blend.

In accordance with aspect 37, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, furthercomprising a recycled material comprising one or more recycled polymers,optionally wherein the one or more recycled polymers comprise one ormore recycled thermoplastics, optionally wherein the one or morerecycled thermoplastics comprise one or more recycled thermoplasticelastomers; optionally wherein the recycled material comprises arecycled material polymeric component consisting of one or more recycledthermoplastics, optionally wherein the recycled material polymericcomponent comprises or consists essentially of one or more recycledthermoplastic elastomers.

In accordance with aspect 38, the present disclosure is directed to themulti-layered film of aspect 37, wherein the recycled material comprisesone or more recycled thermoplastic elastomers, optionally wherein theone or more recycled thermoplastic elastomers comprise one or morereground thermoplastic elastomers, optionally wherein the one or morerecycled or reground thermoplastic elastomers includes a thermoplasticelastomeric material according to any one of aspects 10-19.

In accordance with aspect 39, the present disclosure is directed to themulti-layered film of aspect 36 or 37, wherein the recycled materialfurther comprises one or more recycled second thermoplastics, optionallywherein the one or more recycled second thermoplastics comprise one ormore reground second thermoplastics, optionally wherein the one or morerecycled or reground second thermoplastics include a thermoplasticaccording to any one of aspects 26-29.

In accordance with aspect 40, the present disclosure is directed to themulti-layered film of aspect 39, wherein the recycled material comprisesone or more recycled or reground thermoplastic polyurethane elastomersor one or more recycled or reground thermoplastic ethylene-vinyl alcoholcopolymers or both.

In accordance with aspect 41, the present disclosure is directed to themulti-layered film of aspect 39 or 40, wherein the recycled materialcomprises a blend of the one or more recycled or reground thermoplasticelastomers and one or more second thermoplastics, or wherein therecycled material comprises a blend of one or more thermoplasticelastomers and one or more recycled thermoplastics or one or morerecycled second thermoplastics, optionally wherein the blend is aphase-separated blend, and optionally wherein the phase-separated blendcomprises one or more interfaces between the one or more recycledthermoplastic elastomers and the one or more second thermoplastics.

In accordance with aspect 42, the present disclosure is directed to themulti-layered film of any of aspects 37-41, wherein the recycledmaterial comprises about 99 percent to about 90 percent by weight of theone or more recycled thermoplastic elastomers and about 1 percent toabout 10 percent by weight of the one or more second thermoplasticsbased on a total weight of the recycled material, optionally wherein therecycled material comprises about 99 percent to about 93 percent byweight of the one or more recycled thermoplastic elastomers and about 1percent to about 7 percent by weight of the one or more secondthermoplastics, or about 99 percent to about 95 percent by weight of theone or more recycled thermoplastic elastomers and about 1 percent toabout 5 percent by weight of the one or more second thermoplasticelastomers.

In accordance with aspect 43, the present disclosure is directed to themulti-layered film of any one of aspects 37-42, wherein the recycledmaterial comprises about 99 percent to about 50 percent by weight ofrecycled or reground polymers based on a total weight of recycledmaterial, optionally from about 99 percent to about 75 percent by weightof recycled or reground polymers.

In accordance with aspect 44, the present disclosure is directed to themulti-layered film of any of aspects 38-43, wherein the recycledmaterial further comprises one or more virgin first thermoplasticelastomers, optionally wherein the one or more virgin firstthermoplastic elastomers includes one or more virgin thermoplasticpolyurethane elastomers.

In accordance with aspect 45, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, furthercomprising one or more tie layers, each of the one or more tie layersindividually comprising or consisting essentially of a tie material,wherein the one or more tie layers increase a bond strength between twoadjacent layers.

In accordance with aspect 46, the present disclosure is directed to themulti-layered film of aspect 45, wherein the tie material of each of theone or more tie layers independently comprises or consists essentiallyof a polyurethane, a polyacrylate, an ethylene-acrylate copolymer, amaleic anhydride grafted polyolefin, or any combination thereof,optionally wherein the tie material comprises or consists essentially ofa blended material according to any of aspects 26-36 or a recycledmaterial according to any of aspects 37-44.

In accordance with aspect 47, the present disclosure is directed to themulti-layered film of aspect 45 or 46, wherein the tie material of theone or more tie layers independently comprises or consists essentiallyof one or more thermoplastic polyurethane elastomeric homopolymers orcopolymers, optionally wherein the one or more tie layers comprise orconsist essentially of a polydiene polyol-based thermoplasticpolyurethane.

In accordance with aspect 48, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, furthercomprising one or more structural layers, each of the one or morestructural layers independently comprising or consisting essentially ofa structural layer material, optionally wherein the structural layermaterial comprises or consists essentially of a blended materialaccording to any of aspects 26-36 or a recycled material according toany of aspects 37-44.

In accordance with aspect 49, the present disclosure is directed to themulti-layered film of aspect 48, wherein the structural layer materialof each of the one or more structural layers independently comprises orconsists essentially of a polydiene polyol-based thermoplasticpolyurethane.

In accordance with aspect 50, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, wherein theelastomeric material of the one or more core regions is a firstelastomeric material, wherein the multi-layered film further comprises asecond elastomeric material, and wherein the formed multi-layered filmfurther comprises:

a first structural layer secured to a first side of one of the one ormore core regions, optionally wherein the first structural layercomprises the second elastomeric material and optionally has an averagethickness ranging from about 900 micrometers to about 1990 micrometers;and a second structural layer secured to a second side of the coreregion that is opposing to the first side of the core region, optionallywherein the second structural layer comprises the second elastomericmaterial and optionally has an average thickness ranging from about 900micrometers to about 1990 micrometers.

In accordance with aspect 51, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, furthercomprising one or more cap layers, wherein the one or more cap layerscomprise or consist essentially of a cap layer material, optionallywherein the cap layer material comprises or consists essentially of ablended material according to any of aspects 26-36 or a recycledmaterial according to any of aspects 37-44.

In accordance with aspect 52, the present disclosure is directed to themulti-layered film of aspect 51, wherein the cap layer material of theone or more cap layers comprises or consists essentially of apolyurethane, a polyacrylate, an ethylene-acrylate copolymer, a maleicanhydride grafted polyolefin, or any combination thereof.

In accordance with aspect 53, the present disclosure is directed to themulti-layered film of aspect 50 or 51, wherein the cap layer material ofthe one or more cap layers comprises or consists essentially of athermoplastic polyurethane, optionally a polydiene polyol-basedthermoplastic polyurethane.

In accordance with aspect 54, the present disclosure is directed to themulti-layered film of any one of aspects 51-53, wherein at least one ofthe one or more tie layers is positioned between one of the one or morestructural layers and one of the one or more core regions.

In accordance with aspect 55, the present disclosure is directed to themulti-layered film of any one of aspects 51-54, wherein at least one ofthe one or more structural layers is positioned between one of the oneor more tie layers and one of the one or more cap layers.

In accordance with aspect 56, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, wherein themulti-layered film is a coextruded layered sheet, or a laminated layeredsheet.

In accordance with aspect 57, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, wherein themulti-layered film comprises a first cap layer, a first structurallayer, a first tie layer, a core region, a second tie layer, a secondstructural layer, and a second cap layer, wherein a first cap layerinner surface contacts a first surface of the first structural layer, asecond surface of the first structural layer contacts a first surface ofthe first tie layer, a second surface of the first tie layer contacts afirst surface of the core region, a second surface of the core regioncontacts a first surface of the second tie layer, a second surface ofthe second tie layer contacts a first surface of the second structurallayer, and a second surface of the second structural layer contacts aninner layer of the second cap layer.

In accordance with aspect 58, the present disclosure is directed to themulti-layered film of any one of aspects 45-57, wherein themulti-layered film has a structure of A-B-C-B-A, wherein A represents astructural layer, B represents a tie layer, and C represents a coreregion.

In accordance with aspect 59, the present disclosure is directed to themulti-layered film of any one of aspects 45-57, wherein themulti-layered film has a structure of D-A-B-C-B-A-D, wherein Arepresents a structural layer, B represents a tie layer, C represents acore region, and D represents a cap layer.

In accordance with aspect 60, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, wherein the oneor more core regions has a gas transmission rate of from about 0.3 toabout 1.9 cubic centimeters per square meter per day for nitrogenmeasured at 23 degrees Celsius and 0 percent relative humidity for astructure having a thickness of from about 72 micrometers to about 320micrometers, optionally wherein each of the one or more core regions hasa gas transmission rate of from about 0.3 to about 1.9 cubic centimetersper square meter per day for nitrogen measured at 23 degrees Celsius and0 percent relative humidity.

In accordance with aspect 61, the present disclosure is directed to themulti-layered film of any one of the preceding aspects, wherein themulti-layered film comprises one or more protective layers, each of theone or more protective layers individually comprising or consistingessentially of a protective material, wherein each of the one or moreprotective layers is adjacent to a core region and has a protectivelayer thickness, wherein a combination of the one or more protectivelayers and the adjacent core region has a minimum radius of curvaturewhich is greater than a minimum radius of curvature which causescracking of the core region, or of one or more individual layers withinthe core region.

In accordance with aspect 62, the present disclosure is directed to amethod for manufacturing a multi-layered film, wherein the multi-layeredfilm is a multi-layered film according to any one of aspects 1-61, themethod comprising:

co-extruding the gas-barrier material and the elastomeric material toform the multi-layered film.

In accordance with aspect 63, the present disclosure is directed to themethod of aspect 62, further comprising:

co-extruding at least one tie layer with the multi-layered filmcomprising the core region to form a multi-layered film comprising theone or more core regions and the tie layer.

In accordance with aspect 64, the present disclosure is directed to themethod of aspect 62 or 63, further comprising:

applying at least one structural layer to the multi-layered filmcomprising the core region and the tie layer to form a multi-layeredfilm comprising the one or more core regions, the tie layer, and thestructural layer, wherein the structural layer comprises a structurallayer material according to aspect 48 or 49.

In accordance with aspect 65, the present disclosure is directed to themethod of aspect 62 or 63 further comprising:

co-extruding at least one structural layer with the multi-layered filmcomprising the core region and the tie layer to form a multi-layeredfilm comprising the one or more core regions, the tie layer, and thestructural layer.

In accordance with aspect 66, the present disclosure is directed to themethod of any one of aspects 62-65, further comprising:

co-extruding at least one cap layer with the multi-layered filmcomprising the core region, the tie layer, and the structural layer toform a multi-layered film comprising the core region, the tie layer, thestructural layer, and the cap layer.

In accordance with aspect 67, the present disclosure is directed to amulti-layered film produced by the method of any one of aspects 62-66.

In accordance with aspect 68, the present disclosure is directed to anarticle comprising the multi-layered film of any one of aspects 1-61 or67, wherein the multi-layered film of the article comprises a series ofthree or more layers, including

a first cap layer comprising or consisting essentially of a first caplayer material, the first cap layer including a first cap layer outersurface defining a first outer surface of the multi-layered film, afirst cap layer inner surface opposing the first cap layer outersurface, a first cap layer thickness extending from the first cap layerinner surface to the first cap layer outer surface, wherein the firstcap layer outer surface defines a first exterior surface of the article;

optionally, a second cap layer comprising or consisting essentially of asecond cap layer material, the second cap layer including a second caplayer outer surface defining a second outer surface of the multi-layeredfilm, a second cap layer inner surface opposing the second cap layerouter surface, a second cap layer thickness extending from the secondcap layer inner surface to the second cap layer outer surface,optionally wherein the second cap layer outer surface defines a secondexterior surface of the article; and

the one or more core regions, each of the one or more core regionsincluding a core region first surface, a core region second surface, anda core region thickness extending from the core region first surface tothe core region second surface, wherein each of the one or more coreregions is positioned between the first cap layer inner surface and thesecond cap layer inner surface.

In accordance with aspect 69, the present disclosure is directed to thearticle of aspect 68, wherein, in the multi-layered film, the second caplayer is present and wherein the first cap layer material and the secondcap layer material are substantially the same.

In accordance with aspect 70, the present disclosure is directed to thearticle of aspect 68, wherein, in the multi-layered film, the second caplayer is present and wherein the first cap layer material and the secondcap layer material are different.

In accordance with aspect 71, the present disclosure is directed to thearticle of any one of aspects 68-70, wherein, in the multi-layered film,the first cap layer inner surface is in contact with the core regionfirst surface, or the optional second cap layer inner surface is incontact with the core region second surface, or both.

In accordance with aspect 72, the present disclosure is directed to thearticle of any one of aspects 68-71, wherein the multi-layered film ofthe article is configured as a series of four of more layers includingone or more structural layers, each of the one or more structural layerscomprising a structural layer material and including a structural layerfirst surface, a structural layer second surface opposing the structurallayer first surface, and a structural layer thickness extending from thestructural layer first surface to the structural layer second surface;

optionally wherein at least one of the one or more structural layers ispositioned between the first cap layer and the core region, or betweenthe second cap layer and the core region; or

optionally wherein the one or more structural layers comprise two ormore structural layers, and at least a first one of the two or morestructural layers is positioned between an inner surface of a first caplayer and the first surface of a core region, and at least a second oneof the two or more structural layers is positioned between a secondsurface of a core region and the inner surface of the second cap layer.

In accordance with aspect 73, the present disclosure is directed to thearticle of aspect 72, wherein, in the multi-layered film, a firstsurface of a first one of the structural layers is in contact with theinner surface of the first cap layer, and the second surface of thefirst one of the structural layers is in contact with a first surface ofone of the one or more core regions, or wherein the first surface of asecond one of the one or more structural layers is in contact with thesecond surface of one of the one or more core regions, and the secondsurface of the second one of the structural layers is in contact with aninner surface of the second cap layer, or both.

In accordance with aspect 74, the present disclosure is directed to thearticle of any one of aspects 68-73, wherein, in the multi-layered film,the one or more structural layers comprise or consist essentially of theblended material of any one of aspects 26-36.

In accordance with aspect 75, the present disclosure is directed to thearticle of any one of aspects 68-73, wherein, in the multi-layered film,the one or more structural layers comprise or consist essentially of therecycled material of any one of aspects 37-44.

In accordance with aspect 76, the present disclosure is directed to thearticle of any one of aspects 68-75, wherein the multi-layered film ofthe article is configured as a series of five or more layers includingone or more tie layers, each of the one or more tie layers including atie layer first surface, a tie layer second surface opposing the tielayer first surface, and a tie layer thickness extending from the tielayer first surface to the tie layer second surface;

optionally wherein at least one of the one or more tie layers ispositioned between one of the one or more structural layers and one ofthe one or more core regions, or between the first cap layer and one ofthe one or more structural layers, or between the second cap layer andone of the one or more structural layers, or any combination thereof; or

optionally wherein the one or more tie layers comprise two or more tielayers, and at least a first one of the two or more tie layers ispositioned between a second surface of a first structural layer and afirst layer of a core region, and at least a second one of the two ormore tie layers is positioned between a second surface of a core regionand a first surface of a structural layer.

In accordance with aspect 77, the present disclosure is directed to thearticle of aspect 76, wherein, in the multi-layered film, a firstsurface of a first one of the one or more tie layers is in contact witha second surface of a first one of the one or more structural layers,and the second surface of the first one of the one or more tie layers isin contact with a first surface of a core region; or wherein a firstsurface of a second one of the one or more tie layers is in contact witha second surface of one of the one or more core regions, and the secondsurface of the second one of the one or more tie layers is in contactwith a first surface of a second one of the one or more structurallayers, or both.

In accordance with aspect 78, the present disclosure is directed to thearticle of any one of aspects 76 or 77, wherein the multi-layered filmof the article comprises a first cap layer, a first structural layer, afirst tie layer, a core region, a second tie layer, a second structurallayer, and a second cap layer, wherein the first cap layer inner surfacecontacts the first surface of the first structural layer, the secondsurface of the first structural layer contacts the first surface of thefirst tie layer, the second surface of the first tie layer contacts thefirst surface of the core region, the second surface of the core regioncontacts the first surface of the second tie layer, the second surfaceof the second tie layer contacts the first surface of the secondstructural layer, and the second surface of the second structural layercontacts the inner layer of the second cap layer.

In accordance with aspect 79, the present disclosure is directed to thearticle any one of aspects 68-78, wherein the article is a layeredsheet, optionally wherein the layered sheet is a coextruded layeredsheet, or is a laminated layered sheet.

In accordance with aspect 80, the present disclosure is directed to thearticle of any one of aspects 68-79, wherein the article comprises acushioning element.

In accordance with aspect 81, the present disclosure is directed to thearticle of aspect 80, wherein the multi-layered film forms anexternal-facing layer of the cushioning element.

In accordance with aspect 82, the present disclosure is directed to thearticle of aspect 80 or 81, wherein the multi-layered film is effectiveat retaining a fluid in the cushioning element.

In accordance with aspect 83, the present disclosure is directed to thearticle of any one of aspects 80-82, wherein the cushioning element is acomponent of an article of footwear, apparel, or sporting equipment.

In accordance with aspect 84, the present disclosure is directed to anarticle comprising the multi-layered film of any one of aspects 1-61 or67.

In accordance with aspect 85, the present disclosure is directed to thearticle of aspect 84, wherein the article comprises an article offootwear, a component of an article footwear, an article of apparel, acomponent of an article of apparel, an article of sporting equipment, acomponent of an article of sporting equipment, a personal protectivearticle, a flexible flotation device, a rigid flotation device, amedical device, a prosthetic device, an orthopedic device, anaccumulator, an article of furniture, or a component of an article offurniture.

In accordance with aspect 86, the present disclosure is directed to thearticle of aspect 84, wherein the article comprises a tire or a hose.

In accordance with aspect 87, the present disclosure is directed to amethod of manufacturing a consumer product, the method comprisingaffixing the article of any one of aspects 84-86 to a second component.

In accordance with aspect 88, the present disclosure is directed to aconsumer product produced by the method of aspect 87.

In accordance with aspect 89, the present disclosure is directed to amethod for producing the multi-layered film of any one of aspects 1-61,comprising:

co-extruding gas-barrier material and elastomeric material to form amulti-layered film comprising the one or more core regions.

In accordance with aspect 90, the present disclosure is directed to themethod of aspect 89, further comprising:

applying at least one tie layer to the multi-layered film comprising theone or more core regions to form a multi-layered film comprising the oneor more core regions and the tie layer, wherein the tie layer comprisesa tie material according to aspect 45.

In accordance with aspect 91, the present disclosure is directed to themethod of aspect 89, further comprising:

co-extruding at least one tie layer with the multi-layered filmcomprising the core region to form a multi-layered film comprising theone or more core regions and the tie layer.

In accordance with aspect 92, the present disclosure is directed to themethod of any one of aspects 89-91, further comprising:

applying at least one structural layer to the multi-layered filmcomprising the core region and the tie layer to form a multi-layeredfilm comprising the one or more core regions, the tie layer, and thestructural layer, wherein the structural layer comprises a structurallayer material according to aspect 47.

In accordance with aspect 93, the present disclosure is directed to themethod of aspect 92, further comprising:

co-extruding at least one structural layer with the multi-layered filmcomprising the core region and the tie layer to form a multi-layeredfilm comprising the one or more core regions, the tie layer, and thestructural layer.

In accordance with aspect 94, the present disclosure is directed to themethod of any one of aspects 89-93, further comprising:

applying at least one cap layer to the multi-layered film comprising thecore region, the tie layer, and the structural layer to form amulti-layered film comprising the core region, the tie layer, thestructural layer, and the cap layer, wherein the cap layer comprises acap layer material according to any one of aspects 51-53.

In accordance with aspect 95, the present disclosure is directed to themethod of any one of aspects 89-93, further comprising:

co-extruding at least one cap layer with the multi-layered filmcomprising the core region, the tie layer, and the structural layer toform a multi-layered film comprising the core region, the tie layer, thestructural layer, and the cap layer.

In accordance with aspect 96, the present disclosure is directed to themulti-layered film of any one of aspects 1-61 or 67, further comprisinga decorative element.

In accordance with aspect 97, the present disclosure is directed to amethod for applying a decorative element to the multi-layered film ofany one of aspects 1-61 or 67, wherein the method comprises applying thedecorative element by printing, painting, brushing, or spraying thedecorative element onto the multi-layered film; or dipping themulti-layered film into the decorative element; or pressing thedecorative element and the multi-layered film together, wherein thedecorative element is in the form of a solid, a liquid, or a gas whenapplied to the multi-layered film, optionally wherein the decorativeelement comprises a pigment or a dye or both a pigment and a dye.

In accordance with aspect 98, the present disclosure is directed to themethod of aspect 96 or 97, wherein the decorative element comprisespigments or dyes or both, and the step of applying the decorativeelement onto the multi-layered film comprises curing the decorativeelement on the multi-layered film, optionally wherein the curingcomprises drying the decorative element, or crosslinking the decorativeelement, or infusing at least a portion of the decorative element into apolymeric material of an exterior surface of the multi-layered film, orbonding the decorative element to the exterior surface of themulti-layered film, or any combination thereof.

In accordance with aspect 99, the present disclosure is directed to themethod of aspect 98, wherein the method comprises the step of bondingthe decorative element to the exterior surface of the multi-layeredfilm, and the bonding includes forming an adhesive bond by applying anadhesive to a first side of the decorative element or to the exteriorsurface of the multi-layered film, or both, and then pressing togetherthe first side of the decorative element and the exterior surface of themulti-layered film.

In accordance with aspect 100, the present disclosure is directed to themethod of aspect 98, wherein the method comprises the step of bondingthe decorative element to the exterior surface of the multi-layeredfilm, and the bonding includes forming a thermal bond between athermoplastic material of a first side of the decorative element and athermoplastic material defining the exterior surface of themulti-layered film, by softening or melting at least an outer portion ofone or both of the thermoplastic materials, and pressing the first sideof the decorative element and the exterior surface of the multi-layeredfilm against each other while the one or both of the thermoplasticmaterials are softened or melted, and then re-solidifying the softenedor melted outer portion.

In accordance with aspect 101, the present disclosure is directed to themethod of aspect 98, wherein the decorative element is applied to anexterior surface of the multi-layered film, and, during applying orduring the curing or during both the applying and the curing, thedecorative element infuses into a material defining the exterior surfaceof the multi-layered film, optionally wherein the decorative element isapplied as a solution of a dye.

In accordance with aspect 102, the present disclosure is directed to amulti-layered film comprising a decorative element applied according tothe method of any one of aspects 97-101.

Bladders and Airbags

In one aspect, an airbag can include a first sheet, a second sheet, orboth a first sheet and a second sheet of the multi-layered film that arebonded together (e.g., thermally bonded) to form an internal cavity in aspace between the first and second sheets, where the bond extends aroundat least a portion of a perimeter of the internal cavity. The internalcavity can be inflated with one or more fluids (e.g., one or more gases)during or after the bonding step. In some aspects, the bond extendsaround the entire perimeter of the internal cavity, providing a sealedairbag. In other aspects, the bond extends around only a portion of theentire perimeter (e.g., around most of the entire perimeter) and definesa sealable aperture configured to receive fluid(s)/gases(s) to theinternal cavity. Under each aspect, when inflated and sealed, theresulting airbag is capable of retaining the received fluid(s)/gases(s)in the internal cavity for extended usage due to the gas-barrierproperties of the multi-layered film. In some aspects, the bladder cancomprise a second multi-layered film, optionally wherein the structureof the second multi-layered film differs from the structure of the firstmulti-layered film in number of gas-barrier layers and elastomericlayers, or differs in thickness of gas-barrier layers and elastomericlayers, or differs in both number and thickness of gas-barrier layersand elastomeric layers.

As discussed in more detail below, the multi-layered film includes oneor more core regions, where each of the one or more core regionscomprises multiple layers that alternate between thin gas-barrier layers(each having at least one gas-barrier material) and elastomeric layers(each having at least one elastomeric material). In an aspect, in thecore region, the gas-barrier material(s) of the gas-barrier layers andthe elastomeric material(s) of the elastomeric layers have similarprocessing characteristics and can be co-extruded with reducedinterlayer shear. This allows the alternating gas-barrier layers andelastomeric layers to be co-extended while retaining their structuralintegrities and desired layer thicknesses for use in the resultingmulti-layered films.

In an aspect, to impart good gas-barrier properties, the gas-barriermaterials of the gas-barrier layers are typically less flexible (e.g.,more glass-like) than the elastomeric materials of the elastomericlayers. In particular, the elastomeric materials of the elastomericlayers may have a lower glass transition temperature than thegas-barrier materials of the gas-barrier layers, for example 20 degreesCelsius lower, optionally 50 degrees Celsius lower. As such, thegas-barrier layers of the core region(s) are more susceptible tomicroscopic cracking when subjected to repeated, excessive stress loads,such as those potentially generated during flexing and release of themulti-layered film.

However, in one aspect, it has been found that the use of at least abouttwenty, at least about thirty, or at least about forty gas-barrierlayers, where each gas-barrier layer has an average layer thickness ofless than about 2 micrometers, or from about 0.5 micrometers to about 2micrometers, optionally less than about 0.5 micrometers, and acorresponding number of elastomeric layers such that each core regionalternates between the gas-barrier layers and the elastomeric layers,can increase the flexibility of the core region(s), while maintainingthe durability and gas-barrier properties of the multi-layered film. Assuch, airbags incorporating the multi-layered film can be designed towithstand repeated flexing and release (e.g., by walking, running, andjumping) with reduced or no visually observable cracking, crazing, orhazing over extended usage.

It has been found that the use of at least 20, or at least 30, or atleast 40 gas-barrier layers, where each gas-barrier layer has an averagelayer thickness of less than about 2 micrometers, optionally of lessthan about 0.75 micrometers, or optionally of less than about 0.5micrometers, or in a range of from about 0.5 micrometers to about 2micrometers, optionally in a range of from about 0.01 to about 0.75micrometers, or optionally in a range of from about 0.01 to about 0.5micrometers, and a corresponding number of elastomeric layers such thatin each core region, the gas-barrier layers and the elastomeric layersalternate, can increase the flexibility of the core region(s), whilemaintaining the durability and gas-barrier properties of themulti-layered film. As such, airbags incorporating the multi-layeredfilm can be designed to withstand repeated flexing and release (e.g., bywalking, running, and jumping) with reduced with reduced or no visuallyobservable cracking, crazing, or hazing over extended usage.

In an aspect, the multi-layered films and airbags, bladders, and otherenclosed and/or hollow articles constructed therefrom are configured towithstand repeated flexing and release without cracking, crazing, ordeveloping haze or other significant appearance changes. In an exemplaryaspect, a bladder constructed from sheets comprising the multi-layeredfilms can be incorporated as a cushioning element into a sole structureof an article of footwear. Further in this aspect, actions such aswalking, running, and jumping may cause flexing and release of thebladder; however, bladders and other articles comprising themulti-layered films have a longer useful lifetime than known cushioningelements. In one aspect, disclosed herein is an article comprising thedisclosed multi-layered films. In one aspect, the article is acushioning element. In another aspect, the multi-layered film forms anexternal-facing layer of the cushioning element and is effective atretaining a fluid in the cushioning element. In any of these aspects,the cushioning element is a component of a consumer good such as anarticle of footwear, apparel, or sporting equipment. In another aspect,the cushioning element is a cushioning element for an article offootwear, and the cushioning element for the article of footwear is anairsole.

In another aspect, each of the elastomeric layers can have an averagethickness of from about 2 micrometers to about 8 micrometers, or fromabout 2 micrometers to about 5 micrometers, from about 5 micrometers toabout 8 micrometers, or from about 4 micrometers to about 6 micrometers.

In some aspects, the core region comprises at least 50 gas-barrierlayers, or from about 50 to about 100 gas-barrier layers, from about 60to about 80 gas-barrier layers, or from about 60 to about 70 gas-barrierlayers. In one aspect, the core region comprises at least 50 elastomericlayers, or from about 50 to about 100 elastomeric layers, from about 60to about 80 elastomeric, or from about 60 to about 70 elastomericlayers.

In one aspect, the average total thickness of the core region rangesfrom about 125 to about 200 micrometers and the multi-layered filmfurther includes a first structural layer secured to a first side of thecore region, wherein the first structural layer has an average thicknessof from about 900 micrometers to about 1990 micrometers, optionally fromabout 900 micrometers to about 1500 micrometers, from about 1500micrometers to about 1990 micrometers, or from about 1000 micrometers toabout 1400 micrometers; and a second structural layer secured to asecond side of the core region that is opposite to the first side of thecore region, wherein the second structural layer has an averagethickness of from about 900 micrometers to about 1990 micrometers,optionally from about 900 micrometers to about 1500 micrometers, fromabout 1500 micrometers to about 1990 micrometers, or from about 1000micrometers to about 1400 micrometers.

In another aspect, the structural layer material of each of the one ormore structural layers independently comprises or consists essentiallyof a polydiene polyol-based thermoplastic polyurethane.

In another aspect, the disclosed bladders further include one or morecap layers comprising or consisting essentially of a cap layer material.In another aspect, the cap layer material of the one or more cap layerscomprises or consists essentially of a polyurethane, a polyacrylate, anethylene-acrylate copolymer, a maleic anhydride grafted polyolefin, orany combination thereof. In still another aspect, each cap layer has athickness of from about 5 micrometers to about 25 micrometers, or fromabout 5 micrometers to about 10 micrometers, or from about 10micrometers to about 20 micrometers.

In still another aspect, the disclosed bladders further include one ormore tie layers, each of the one or more tie layers comprising orconsisting essentially of a tie material, wherein the one or more tielayers increase a bond strength between two adjacent layers. In anotheraspect, the tie material of each of the one or more tie layersindependently comprises or consists essentially of a polyurethane, apolyacrylate, an ethylene-acrylate copolymer, a maleic anhydride graftedpolyolefin, or any combination thereof. In still another aspect, each ofthe one or more tie layers has a thickness of from about 5 micrometersto about 20 micrometers, or from about 5 micrometers to about 10micrometers, or from about 10 micrometers to about 20 micrometers.

The multi-layered films, airbags, or bladders disclosed herein maycomprise or consist of one or more gas-barrier layers. As used herein, agas-barrier layer is understood to be a membrane comprising orconsisting essentially of a gas-barrier material, where the thickness ofthe gas-barrier material in the gas-barrier layer is at least 0.01microns. The gas-barrier material comprises or consists essentially ofone or more gas-barrier compounds, including one or more polymericgas-barrier compounds (i.e., gas-barrier polymers), or one or morenon-polymeric gas-barrier compounds, or a combination of one or moregas-barrier polymers and one or more non-polymeric gas-barriercompounds. Polymeric and non-polymeric gas-barrier compounds have theability to restrict the passage of gasses through the material. While nopolymer offers an infinite gas-barrier, gas-barrier polymers typicallyexhibit higher level of crystallinity at room temperature, and higherlevels of intramolecular hydrogen bonding, as compared with polymerswhich are poor gas-barriers. Many examples of gas-barrier polymers andnon-polymeric gas-barrier compounds are known in the art. The one ormore gas-barrier compounds can include one or more gas-barrier polymers,optionally one or more thermoplastic gas-barrier polymers. In themulti-layered film, one or more gas-barrier layers may be used alone, orin combination with other layers formed of other materials, includingother polymeric materials such as elastomeric materials. The otherlayers formed of elastomeric materials are referred to as “elastomericlayers,” and the elastomeric material comprises or consists essentiallyof one or more elastomers, optionally one or more thermoplasticelastomers. A “core region” is an internal region of the multi-layeredfilm in which the one or more gas-barrier layers are located. In manyaspects, the core region comprises a plurality of individual gas-barrierlayers each alternating with a layer formed of other materials.Optionally, the core region comprises a plurality of gas-barrier layerseach having an average thickness of less than or equal to about 0.75micrometers, each of the gas-barrier layers alternating with anelastomeric layer, optionally at least 20 individual gas-barrier layerseach alternating with an elastomeric layer. When used alone or incombination with other materials (optionally, elastomeric materials) inan airbag or bladder, the core region resiliently retains the gas.Depending upon the structure and use of the airbag or bladder, the coreregion may retain the gas at a pressure which is above, at, or belowatmospheric pressure. Examples of gasses include air, oxygen gas (02),and nitrogen gas (N2), as well as inert gasses. In one aspect, thegas-barrier layer is a nitrogen gas-barrier layer.

The gas transmission rate of the core region of the multi-layered filmor of the entire multi-layered film, such as the oxygen gas or nitrogengas transmission rate, can be measured using ASTM D1434. Thus, as usedherein, the term “gas-barrier” material may refer to a material formingone or more layers in a core region of a multi-layered film, the coreregion of the multi-layered film having a total thickness less than orequal to 500 micrometers, optionally less than or equal to 300micrometers, or less than or equal to 200 micrometers, or less than orequal to 100 micrometers, in which the core region, or the multi-layeredfilm as a whole, has an oxygen gas or nitrogen gas transmission rate asmeasured using ASTM D1434 of less than or equal to about 4 cubiccentimeters per square meter per day, optionally less than or equal toabout 3 cubic centimeters per square meter per day.

In one aspect, the gas-barrier layer comprise a multi-layered filmcomprising a plurality of layers, the plurality of layers comprising oneor more gas-barrier layers, the one or more gas-barrier layerscomprising a gas-barrier material, the gas-barrier material comprisingor consisting essentially of one or more gas-barrier compounds. Themulti-layered film comprises at least 5 layers or at least 10 layers.Optionally, the multi-layered film comprises from about 5 to about 200layers, from about 10 to about 100 layers, from about 20 to about 80layers, from about 20 to about 50 layers, or from about 40 to about 90layers. In particular, the multi-layered film may comprise about 20 ormore gas-barrier layers, or about 30 or more gas-barrier layers, orabout 40 or more gas-barrier layers, optionally fewer than 70gas-barrier layers.

In one aspect of a multi-layered film, the plurality of layers includesa series of alternating layers, in which the alternating layers includetwo or more gas-barrier layers, each of the two or more gas-barrierlayers individually comprising a gas-barrier material, the gas-barriermaterial comprising or consisting essentially of one or more gas-barriercompounds. In the series of alternating layers, adjacent layers areindividually formed of materials which differ from each other at leastin their chemical compositions based on the individual componentspresent (e.g., the materials of adjacent layers may differ based onwhether or not a gas-barrier compound is present, or differ based onclass or type of gas-barrier compound present), the concentration of theindividual components present (e.g., the materials of adjacent layersmay differ based on the concentration of a specific type of gas-barriercompound present), or may differ based on both the components presentand their concentrations.

The plurality of layers of the multi-layered film can include firstgas-barrier layers comprising a first gas-barrier material and secondgas-barrier layers comprising a second gas-barrier material, wherein thefirst and second gas-barrier materials differ from each other based asdescribed above. The first gas-barrier material can be described ascomprising a first gas-barrier component consisting of all thegas-barrier compounds present in the first gas-barrier material, and thesecond gas-barrier material can be described as comprising a secondgas-barrier material component consisting of all the gas-barriercompounds present in the second gas-barrier material. The firstgas-barrier component may consist only of one or more gas-barrierpolymers, and the second gas-barrier component may consist only of oneor more inorganic gas-barrier compounds. The first gas-barrier componentmay consist of a first one or more gas-barrier polymers, and the secondgas-barrier component may consist of a second one or more gas-barrierpolymers, wherein the first one or more gas-barrier polymers differ fromthe second one or more gas-barrier polymers in polymer class, type, orconcentration. The first gas-barrier component and the secondgas-barrier component may both include the same type of gas-barriercompound, but the concentration of the gas-barrier compound may differ,optionally the concentrations may differ by at least 5 weight percentbased on the weight of the gas-barrier material. In these multi-layeredfilms, the first gas-barrier layers and the second gas-barrier layersmay alternate with each other, or may alternate with additionalgas-barrier layers (e.g., third gas-barrier layers comprising a thirdgas-barrier material, fourth gas-barrier layers comprising a fourthgas-barrier material, etc., wherein each of the first, second, third andfourth, etc., gas-barrier materials may differ from each other asdescribed above).

The gas-barrier material comprises or consists essentially of one ormore gas-barrier compounds. The one or more gas-barrier compounds maycomprise one or more gas-barrier polymers, or may comprise one or morenon-polymeric gas-barrier compounds, including one or more inorganicgas-barrier compounds, or may comprise a combination of at least onegas-barrier polymer and at least one non-polymeric gas-barrier compound.The combination of at least one gas-barrier polymer and at least onenon-polymeric gas-barrier compound, including at least one inorganicgas-barrier compound, may comprise a blend or mixture, or may comprise acomposite in which fibers, particles, or platelets of the non-polymericgas-barrier compound are surrounded by the gas-barrier polymer.

The gas-barrier material may comprise or consist essentially of one ormore inorganic gas-barrier compounds. The one or more inorganicgas-barrier compounds may take the form of fibers, particulates,platelets, or combinations thereof. The fibers, particulates, plateletsmay comprise or consist essentially of nanoscale fibers, particulates,platelets, or combinations thereof. Examples of inorganic gas-barriercompounds include carbon fibers, glass fibers, glass flakes, silicas,silicates, calcium carbonate, clay, mica, talc, carbon black,particulate graphite, metallic flakes, and combinations thereof. Theinorganic gas-barrier component may comprise or consist essentially ofone or more clays. Examples of suitable clays include bentonite,montmorillonite, kaolinite, and mixtures thereof. The inorganicgas-barrier component may consist of clay. Optionally, the gas-barriermaterial may further comprise one or more additional ingredients, suchas a polymer, processing aid, colorant, or any combination thereof. Inaspects where the gas-barrier material comprises or consists essentiallyof one or more inorganic barrier compounds, the gas-barrier material maybe described as comprising an inorganic gas-barrier component consistingof all inorganic gas-barrier compounds present in the gas-barriermaterial. When one or more inorganic gas-barrier compounds are includedin the gas-barrier material, the total concentration of the inorganicgas-barrier component present in the gas-barrier material can be lessthan 60 weight percent, or less than 40 weight percent, or less than 20weight percent of the total composition. Alternatively, the gas-barriermaterial may consist essentially of the one or more inorganicgas-barrier materials.

The gas-barrier compound may comprise or consist essentially of one ormore gas-barrier polymers. The one or more gas-barrier polymers mayinclude one or more thermoplastic polymers. The gas-barrier material maycomprise or consist essentially of one or more thermoplastic polymers,meaning that the gas-barrier material comprises or consists essentiallyof a plurality of thermoplastic polymers, including thermoplasticpolymers which are not gas-barrier polymers. In another example, thegas-barrier material may comprise or consist essentially of one or morethermoplastic gas-barrier polymers, meaning that all the polymerspresent in the gas-barrier material are thermoplastic gas-barrierpolymers. The gas-barrier material can be described as comprising apolymeric component consisting of all polymers present in thegas-barrier material. For example, the polymeric component of thegas-barrier material may consist of a single class of gas-barrierpolymer, such as, for example, one or more polyolefins, or can consistof a single type of gas-barrier polymer, such as one or moreethylene-vinyl alcohol copolymers. Optionally, the gas-barrier materialmay further comprise one or more non-polymeric additives, such as one ormore fillers, processing aids, colorants, or any combination thereof.

Many gas-barrier polymers are known in the art. Examples of gas-barrierpolymers include vinyl polymers such as vinylidene chloride polymers,acrylic polymers such as acrylonitrile polymers, polyamides, epoxypolymers, amine polymers, polyolefins such as polyethylenes andpolypropylenes, copolymers thereof, such as ethylene-vinyl alcoholcopolymers, and mixtures thereof. Examples of thermoplastic gas-barrierpolymers include thermoplastic vinyl homopolymers and copolymers,thermoplastic acrylic homopolymers and copolymers, thermoplastic aminehomopolymers and copolymers, thermoplastic polyolefin homopolymers andcopolymers, and mixtures thereof. The one or more gas-barrier polymersmay comprise or consist essentially of one or more thermoplasticpolyethylene copolymers, such as, for example, one or more thermoplasticethylene-vinyl alcohol copolymers. The one or more ethylene-vinylalcohol copolymers may include from about 28 mole percent to about 44mole percent ethylene content, or from about 32 mole percent to about 44mole percent ethylene content. The one or more gas-barrier polymers maycomprise or consist essentially of one or more polyethyleneimines,polyacrylic acids, polyethyleneoxides, polyacrylamides, polyamidoamines,or any combination thereof.

In another aspect, in addition to the one or more gas-barrier layers(e.g., including first gas-barrier layers, second gas-barrier layers,etc.), the multi-layered film further comprises one or more secondlayers, the one or more second layers comprising a second material.Optionally, the second material comprises one or more polymers. The oneor more gas-barrier layers may include a plurality of gas-barrier layersalternating with a plurality of second layers. Each of the one or morebarrier layers may be positioned between two second layers (e.g., withone second layer positioned on a first side of the barrier layer, andanother second layer on a second side of the gas-barrier layer, thesecond side opposing the first side).

Depending upon the class of gas-barrier compounds used and the intendeduse of the multi-layered film, the second material may have a higher gastransmittance rate than the gas-barrier material, meaning that thesecond material is a poorer gas-barrier than the gas-barrier material.In some aspects, the one or more second layers act as substrates for theone or more gas-barrier layers, and may serve to increase the strength,elasticity, and/or durability of the multi-layered film. Alternativelyor additionally, the one or more second layers may serve to decrease theamount of gas-barrier material(s) needed, thereby reducing the overallmaterial cost. Even when the second material has a relatively high gastransmittance rate, the presence of the one or more second layers,optionally when the one or more second layers are positioned between oneor more barrier layers, may help maintain the overall gas-barrierproperties of the film by increasing the distance between cracks in thegas-barrier layers, thereby increasing the distance gas molecules musttravel between cracks in the barrier layers in order to pass through themulti-layered film. While small fractures or cracks in the gas-barrierlayers of a multi-layered film may not significantly impact the overallbarrier properties of the film, using thinner gas-barrier layers, orusing a larger number of thinner gas-barrier layers, can avoid or reducevisible cracking, crazing, or hazing of the multi-layered film. The oneor more second layers may include, but are not limited to, a tie layerlocated between and promoting adhesion between two different layers ofthe multi-layered film, a structural layer providing mechanical supportto the multi-layered film, a bonding layer including a bonding materialsuch as a hot melt adhesive material to an exterior surface of themulti-layered film, a cap layer providing protection to an exteriorsurface of the multi-layered film, and any combination thereof.

The second material may be an elastomeric material comprising orconsisting essentially of at least one elastomer. As used herein, theterm elastomer may refer to a material having an elongation at break ofgreater than 400 percent, determined in accordance with ASTM D-412-98 at25 degrees Celsius. Optionally, the term elastomer may refer to amaterial that, when formed into a plaque, has a break strength of from10 to 35 kilogram-force, such as from about 10 to about 25kilogram-force, from about 10 to about 20 kilogram-force, from about 15to about 35 kilogram-force, or from about 20 to about 30 kilogram-force.Optionally, the tensile breaking strength or ultimate strength of anelastomer, if adjusted for cross-sectional area, may be greater than 70kilogram-force per square centimeter, or greater than 80 kilogram-forceper square centimeter. Optionally, an elastomer, when formed into aplaque, has a strain to break of from 450 percent to 800 percent, orfrom 500 to 800 percent, or from 500 to 750 percent, or from 600 to 750percent, or from 450 to 700 percent. As another option, an elastomerplaque may have a load at 100 percent strain of from 3 to 8kilogram-force per millimeter, or of about 3 to about 7 kilogram-forceper millimeter, about 3.5 to about 6.5 kilogram-force per millimeter, orabout 4 to about 5 kilogram-force per millimeter. Optionally, theelastomer plaque has a toughness of from 850 kilogram·millimeters to2200 kilogram·millimeters, or of from about 850 kilogram·millimeters toabout 2000 kilogram·millimeters, or of from about 900kilogram·millimeters to about 1750 kilogram·millimeters, or of fromabout 1000 kilogram·millimeters to about 1500 kilogram·millimeters, orof from about 1500 kilogram·millimeters to about 2000kilogram·millimeters. Optionally, the elastomer plaque has a stiffnessof from about 35 to about 155, or of from about 50 to about 150, or offrom about 50 to about 100, or of from about 50 to about 75, or of fromabout 60 to about 155, or of from about 80 to about 150. Optionally, theelastomer plaque has a tear strength of from about 35 to about 80, or offrom about 35 to about 75, or of from about 40 to about 60, or of fromabout 45 to about 50. Many gas-barrier compounds are brittle and/orrelatively inflexible, and so the one or more gas-barrier layers may besusceptible to cracking when subjected to repeated, excessive stressloads, such as those potentially generated during flexing and release ofa multi-layered film. Thus, the elastomeric material may have a lowerglass transition temperature than that of the gas-barrier material (whenit comprises one or more polymers), for example 20 degrees Celsiuslower, optionally 50 degrees Celsius lower. A multi-layered film whichincludes one or more gas-barrier layers alternating with second layersof an elastomeric material results in a multi-layered film that isbetter able to withstand repeated flexing and release while maintainingits gas-barrier properties, as compared to a film without theelastomeric second layers present.

In one aspect, the second material comprises or consists essentially ofone or more polymers. As used herein, the one or more polymers presentin the second material are referred to herein as one or more “secondpolymers” or a “second polymer,” as these polymers are present in thesecond material. References to “second polymer(s)” are not intended toindicate that a “first polymer” is present, either in the secondmaterial, or in the multi-layered film as a whole, although, in manyaspects, multiple classes or types of polymers are present. In oneaspect, the second material comprises or consists essentially of one ormore thermoplastic polymers. In another aspect, the second materialcomprises or consists essentially of one or more elastomeric polymers.In yet another aspect, the second material comprises or consistsessentially of one or more thermoplastic elastomers. The second materialcan be described as comprising a polymeric component consisting of allpolymers present in the second material. In one example, the polymericcomponent of the second material consists of one or more elastomers.Optionally, the second material can further comprise one or morenon-polymeric additives, such as fillers, processing aids, and/orcolorants.

Many polymers which are suitable for use in the second material areknown in the art. Exemplary polymers which can be included in the secondmaterial (e.g., second polymers) include polyolefins, polyamides,polycarbonates, polyimines, polyesters, polyacrylates, polyesters,polyethers, polystyrenes, polyureas, and polyurethanes, includinghomopolymers and copolymers thereof (e.g., polyolefin homopolymers,polyolefin copolymers, etc.), and combinations thereof. In one example,the second material comprises or consists essentially of one or morepolymers chosen from polyolefins, polyamides, polyesters, polystyrenes,and polyurethanes, including homopolymers and copolymers thereof, andcombinations thereof. In another example, the polymeric component of thesecond material consists of one or more thermoplastic polymers, or oneor more elastomers, or one or more thermoplastic elastomers, includingthermoplastic vulcanizates. Alternatively, the one or more secondpolymers can include one or more thermoset or thermosettable elastomers,such as, for example, natural rubbers and synthetic rubbers, includingbutadiene rubber, isoprene rubber, silicone rubber, and the like.

Polyolefins are a class of polymers which include monomeric unitsderived from simple alkenes, such as ethylene, propylene, and butene.Examples of thermoplastic polyolefins include polyethylene homopolymers,polypropylene homopolymers, polypropylene copolymers (includingpolyethylene-polypropylene copolymers), polybutene, ethylene-octenecopolymers, olefin block copolymers, propylene-butane copolymers, andcombinations thereof, including blends of polyethylene homopolymers andpolypropylene homopolymers. Examples of polyolefin elastomers includepolyisobutylene elastomers, poly(alpha-olefin) elastomers, ethylenepropylene elastomers, ethylene propylene diene monomer elastomers, andcombinations thereof.

Polyamides are a class of polymers which include monomeric units linkedby amide bonds. Naturally-occurring polyamides include proteins such aswool and silk, while synthetic amides include polymers such as nylonsand aramids. The one or more second polymers can include thermoplasticpolyamides such as nylon 6, nylon 6-6, and/or nylon-11, as well asthermoplastic polyamide copolymers.

Polyesters are a class of polymers which include monomeric units derivedfrom an ester functional group, and are commonly made by condensingdibasic acids such as, for example, terephthalic acid, with one or morepolyols. In one example, the second material can comprise or consistessentially of one or more thermoplastic polyester elastomers. Examplesof polyester polymers include homopolymers such as polyethyleneterephthalate, polybutylene terephthalate, andpoly-1,4-cyclohexylene-dimethylene terephthalate, as well as copolymerssuch as polyester polyurethanes.

Styrenic polymers are a class of polymers which include monomeric unitsderived from styrene. The one or more second polymers can comprise orconsist essentially of styrenic homopolymers, styrenic randomcopolymers, styrenic block copolymers, or combinations thereof. Examplesof styrenic polymers include styrenic block copolymers, such asacrylonitrile butadiene styrene block copolymers, styrene acrylonitrileblock copolymers, styrene ethylene butylene styrene block copolymers,styrene ethylene butadiene styrene block copolymers, styrene ethylenepropylene styrene block copolymers, styrene butadiene styrene blockcopolymers, and combinations thereof.

Polyurethanes are a class of polymers which include monomeric unitsjoined by carbamate linkages. Polyurethanes are most commonly formed byreacting a polyisocyanate (e.g., a diisocyanate or a triisocyanate) witha polyol (e.g., a diol or triol), optionally in the presence of a chainextender. The monomeric units derived from the polyisocyanate are oftenreferred to as the hard segments of the polyurethane, while themonomeric units derived from the polyols are often referred to as thesoft segments of the polyurethane. The hard segments can be derived fromaliphatic polyisocyanates, or from organic isocyanates, or from amixture of both. The soft segments can be derived from saturatedpolyols, or from unsaturated polyols such as polydiene polyols, or froma mixture of both. When the multi-layered film is to be bonded tonatural or synthetic rubber, including soft segments derived from one ormore polydiene polyols can facilitate bonding between the rubber and thefilm when the rubber and the film are crosslinked in contact with eachother, such as in a vulcanization process.

Examples of suitable polyisocyanates from which the hard segments of thepolyurethane can be derived include hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), butylenediisocyanate (BDI),bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylenediisocyanate (TMDI), bisisocyanatomethylcyclohexane,bisisochanatomethyltricyclodecane, norbornane diisocyanate (NDI),cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexhylmethane diisocyanate(H12MDI), diisocyanatododecane, lysine diisocyanate, toluenediisocyanate (TDI), TDI adducts with trimethylolpropane (TMP), methylenediphenyl diisocyanate (MDI), xylylene diisocyanate (XDI),tetramethylxylylene diisocyanate (TMXDI), hydrogenated xylylenediisocyanate (HXDI), naphthalene 1,5-diisocyanate (NDI),1,5-tetrahydronaphthalene diisocyanate, para-phenylene diisocyanate(PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 4,4′-dibenzyldiisocyanate (DBDI), 4-chloro-1,3-phenylene diisocyanate, and anycombination thereof. In one aspect, the polyurethane comprises orconsists essentially of hard segments derived from toluene diisocyanate(TDI), or from methylene diphenyl diisocyanate (MDI), or from both.

The soft segments of the polyurethane can be derived from a wide varietyof polyols, including polyester polyols, polyether polyols,polyester-ether polyols, polycarbonate polyols, polycaprolactonepolyethers, and combinations thereof. In one aspect, the polyurethanecomprises or consist essentially of monomeric units derived from C₄-C₁₂polyols, or C₆-C₁₀ polyols, or C₈ or lower polyols, meaning polyols with4 to 12 carbon molecules, or with 6 to 10 carbon molecules, or with 8 orfewer carbon molecules in their chemical structures. In another aspect,the polyurethane comprises or consists essentially of monomeric unitsderived from polyester polyols, polyester-ether polyols, polyetherpolyols, or any combination thereof. In yet another aspect, thepolyurethane comprises or consists essentially of soft segments derivedfrom polyols or diols having polyester functional units. The softsegments derived from polyols or diols having polyester functional unitscan comprise about 10 to about 50, or about 20 to about 40, or about 30weight percent of the soft segments present in the polyurethane.

The multi-layered film can be produced by various means such asco-extrusion, lamination, layer-by-layer deposition, or the like. Whenco-extruding one or more barrier layers alone or with one or more secondlayers, selecting materials (e.g., a first barrier material and a secondbarrier material, or a single barrier material and a second material)having similar processing characteristics such as melt temperature andmelt flow index, can reduce interlayer shear during the extrusionprocess, and can allow the alternating barrier layers and second layersto be co-extruded while retaining their structural integrities anddesired layer thicknesses. In one example, the one or more barriermaterials and, optionally, the second material when used, can beextruded into separate individual films, which can then be laminatedtogether to form the multi-layered film.

The multi-layered film can be produced using a layer-by-layer depositionprocess. A substrate, which optionally can comprise a second material ora barrier material, can be built into a multi-layered film by depositinga plurality of layers onto the substrate. The layers can include one ormore barrier layers (e.g., first barrier layers, second barrier layers,etc.). Optionally, the layers can include one or more second layers. Theone or more barrier layers and/or second layers can be deposited by anymeans known in the art such as, for example, dipping, spraying, coating,or another method. The one or more barrier layers can be applied usingcharged solutions or suspensions, e.g., cationic solutions orsuspensions or anionic solutions or suspensions, including a chargedpolymer solution or suspension. The one or more barrier layers can beapplied using a series of two or more solutions having opposite charges,e.g., by applying a cationic solution, followed by an anionic solution,followed by a cationic solution, followed by an anionic solution, etc.

The barrier layers, including the multi-layered film, have an overallthickness of from about 40 micrometers to about 500 micrometers, orabout 50 micrometers to about 400 micrometers, or about 60 micrometersto about 350 micrometers. In one aspect, each individual layer of theplurality of layers of the multi-layered film has a thickness of fromabout 0.001 micrometers to about 10 micrometers. For example, thethickness of an individual barrier layer can range from about 0.001micrometers to about 3 micrometers thick, or from about 0.5 micrometersto about 2 micrometers thick, or from about 0.5 micrometers to about 1micrometer thick; optionally less than or equal to 0.75 micrometersthick, or less than or equal to 0.5 micrometers thick, or in a range offrom about 0.01 micrometers to about 0.75 micrometers thick, preferablyin a range of from about 0.01 micrometers to about 0.5 micrometersthick. The thickness of an individual second layer can range from about2 micrometers to about 8 micrometers thick, or from about 2 micrometersto about 4 micrometers thick.

In a further aspect, thickness of the film and/or their individuallayers can be measured by any method known in the art such as, forexample, ASTM E252, ASTM D6988, ASTM D8136, or using light microscopy orelectron microscopy.

In some aspects, the barrier layers, including the multi-layered film,have a Shore hardness of from about 35 A to about 95 A, optionally fromabout 55 A to about 90 A. In these aspects, hardness can be measuredusing ASTM D2240 using the Shore A scale.

In one aspect, when a co-extrusion process is used to form the barrierlayer from a plurality of alternating barrier layers and second layers,the barrier material has a melt flow index of from about 5 to about 7grams per 10 minutes at 190 degrees Celsius when using a weight of 2.16kilograms, while the second material has a melt flow index of from about20 to about 30 grams per 10 minutes at 190 degrees Celsius when using aweight of 2.16 kilograms. In a further aspect, the melt flow index ofthe barrier material is from about 80 percent to about 120 percent ofthe melt flow index of the barrier material per 10 minutes when measuredat 190 degrees Celsius when using a weight of 2.16 kilograms. In any ofthese aspects, melt flow index can be measured using ASTM D1238.Alternatively or additionally, the barrier material or the secondmaterial or both have a melting temperature of from about 165 degreesCelsius to about 183 degrees Celsius, or from about 155 degrees Celsiusto about 165 degrees Celsius. In one such example, the barrier materialhas a melting temperature of from about 165 degrees Celsius to about 183degrees Celsius, while the second material has a melting temperature offrom about 155 degrees Celsius to about 165 degrees Celsius. Further inthese aspects, melting temperature can be measured using ASTM D3418.

In an aspect, the multi-layered film exhibits a low gas-transmissionrate such that airbags incorporating the multi-layered film can beinflated and sealed for extended use. Such airbags can provide goodcushioning and support when incorporated into consumer products (e.g.,as airsoles for footwear). In a further aspect, the level of cushioningor support does not significantly decrease over an extended period oftime once the airbags are inflated with a gas, due to the low gastransmission rate of the multi-layered film, which substantially reducesthe escape of the inflation gas.

In one aspect, the airbag internal cavity is inflated to a positivepressure, i.e., has an inflation internal pressure above about 15 poundsper square inch (about 100 kilopascals). In further aspects, airbaginternal cavity has an inflation internal pressure ranging from about 17pounds per square inch (about 117 kilopascals) to about 30 pounds persquare inch (about 207 kilopascals). In further aspects, airbag internalcavity has an inflation internal pressure ranging from about 20 poundsper square inch (about 138 kilopascals) to about 22 pounds per squareinch (about 152 kilopascals). In one aspect, after 2 years of use, theairbag internal cavity still has an internal pressure of at least about60 percent of the inflation internal pressure. In further aspects, after2 years of use, the airbag internal cavity still has an internalpressure of at least about 70 percent of the inflation internalpressure.

In some aspects, the airbag has a gas transmission rate of no more than120 percent of an original gas transmission rate after 320,000 KIMcycles, where KIM cycles are performed using the KIM Test Protocoldefined in the Property Analysis and Characterization Procedures sectionincluded herein. In one aspect, the bladder has a gas transmission rateranging from about 0.5 to about 2 cubic centimeters per square meter perday for nitrogen measured at 23 degrees Celsius and 0 percent relativehumidity for a film having a thickness ranging from 72 micrometers to320 micrometers after from 0 KIM cycles to 320,000 KIM cycles. In oneaspect, the airbag does not exhibit crazing or cracking after at least350,000 KIM cycles, or after at least 400,000 KIM cycles.

In some embodiments, the multi-layered film may also include additionallayers on one or both opposing sides of the core region(s). Forinstance, the multi-layered film may include one or more thickerstructural layers to increase the structural integrity and durability ofthe multi-layered film during use in articles, such as airsoles forfootwear. Additionally or alternatively, the multi-layered film may alsoinclude one or more cap layers to improve abrasion resistance, assist inairbag formation (e.g., during thermoforming or blow molding), toimprove bonding to other article components, to improve surfaceproperties for printing graphics and indicia, to improve visualaesthetics and/or tactile properties, water resistance, and the like.

As shown in FIGS. 1 and 2 , the footwear 1010 is an example article offootwear that incorporates the multi-layered film of the presentdisclosure. As shown in FIG. 1 , the article of footwear 1010 can bedivided lengthwise into one or more regions along a longitudinal axisA1010, such as into a forefoot region 1012, a mid-foot region 1014, anda heel region 1016. The forefoot region 1012 can be further described asincluding a toe portion corresponding to a portion of the footwear 1010that surrounds the phalanges of a wearer's foot when worn, and a ballportion corresponding to a portion of the footwear 1010 that surroundsthe metatarsophalangeal (MTP) joint of the wearer's foot when worn. Themid-foot region 1014 corresponds with a portion surrounding an arch areaof the wearer's foot when worn, and the heel region 1016 correspondswith portions of the footwear 1010 surrounding rear portions of thewearer's foot, including the calcaneus bone, when worn.

The footwear 1010 can further include an anterior end 1018 associatedwith a forward-most location of the forefoot region 1012, and aposterior end 1020 corresponding to a rearward-most location of the heelregion 1016. As further shown in FIG. 1 , the longitudinal axis A1010 ofthe footwear 1010 extends along the length of the footwear 1010 from theanterior end 1018 to the posterior end 1020, and generally divides thefootwear 1010 into a medial side 1022 and a lateral side 1024.Accordingly, the medial side 1022 and the lateral side 1024 respectivelycorrespond with opposite sides of the footwear 1010 and extend throughthe regions 1012, 1014, and 1016.

The footwear 1010 also includes an upper 1026 and a sole structure 1028,where the upper 1026 forms a structure that is configured to cover someor all of a wearer's foot and can fit the wearer's foot to the solestructure 1028. The upper 1026 includes an interior surface (not shown)that defines an interior void configured to receive and secure awearer's foot for support on the sole structure 1028. The interior voidcan be accessed at an ankle opening 1026 a and can be shaped and sizedto match and fit the wearer's foot. For instance, the upper 1026 canextend over the instep and toe areas of the wearer's foot (at theforefoot region 1012), along medial and lateral sides of the wearer'sfoot (at the mid-foot region 1014), and around the heel area of thewearer's foot (at the heel region 1016).

The upper 1026 may be formed from one or more components that can bestitched, adhesively bonded, thermally bonded, or otherwise together toform the interior void, such as mesh, textiles, foam, leather, andsynthetic leather. The materials may be selected and located to impartproperties of durability, air-permeability, wear-resistance,flexibility, comfort, and the like. More specific examples of suitablematerials for the upper 1026 are discussed below.

The upper 1026 can also have any suitable design, shape, size, and/orcolorway for footwear applications. For example, in certain aspects,e.g., if the footwear 1010 is a basketball shoe, then the upper 1026 canbe a high-top profile that is shaped to provide high support to awearer's ankle. Alternatively, in certain aspects, e.g., if footwear1010 is a running shoe, then the upper 1026 can have a low-top profile.

In the example shown in FIGS. 1 and 2 , the sole structure 1028 includesa midsole 1030 configured to provide cushioning, support, and aestheticcharacteristics, and an outsole 1032 configured to provide aground-engaging surface of the footwear 1010. In the shown embodiment,the midsole 1030 of the sole structure 1028 is further divided intomultiple sub-components that can provide different forms of cushioning,support, and aesthetics, such as a chassis 1034 and an airsole 1036.

The chassis 1034 can be attached to the upper 1026 to provide aninterface between the upper 1026 and the airsole 1036. In the embodimentillustrated in FIGS. 1 and 2 , the chassis 1034 is a single-componentchassis formed from one or more resilient materials, such as foamsand/or rubbers, to impart properties of cushioning, responsiveness, andenergy distribution to the wearer's foot.

In the shown embodiment, the chassis 1034 is depicted as having asingle, full-length component extending from the forefoot region 1012 tothe heel region 1016. Alternatively, the chassis 1034 may includemultiple components, such as a first component extending from theforefoot region 1012 to the mid-foot region 1014 and a second componentextending from the mid-foot region 1014 to the heel region 1016. In yetfurther alternative aspects, the chassis 1034 may include multiplecomponents providing zonal regions of cushioning and/or rigid support atforefoot region 1012, midfoot region 1014, and/or heel region 1016. Thecomponent(s) of the chassis 1034 may be pre-formed from any suitableresilient materials (e.g., foams and rubbers) and/or rigid materials(e.g., plates and molded parts). In embodiments incorporating resilientmaterials, the component(s) of the chassis 1034 can include molded foamparts, loose foam beads retained in carrier shells, fused foam beadparts (e.g., by compression molding or steam chest molding), foam beadsentrapped in a resilient polymeric resin matrix, and the like to impartproperties of cushioning, responsiveness, support, and energydistribution to the wearer's foot.

Examples of suitable resilient materials for foams include thermoplasticelastomers such as, for example, thermoplastic elastomeric polyolefinhomopolymers or copolymers, thermoplastic elastomeric polyamidehomopolymers or copolymers, thermoplastic elastomeric polyesterhomopolymers or copolymers, thermoplastic elastomeric polyurethanehomopolymers or copolymers, thermoplastic elastomeric styrenichomopolymers or copolymers, or any combination thereof. These materialsmay also include one or more additives, such blowing agents,cross-linking agents, colorants, fillers, and the like. Suitablechemical blowing agents include azo compounds such as azodicarbonamide,sodium bicarbonate, isocyanate, and combinations thereof. Alternatively,the foams of the chassis 1034 may be produced using one or more physicalblowing agents that can phase transition to gases based on a change intemperature and/or pressure. Suitable cross-linking agents (forcross-linked foams) include peroxide-based crosslinking agents such asdicumyl peroxide. Suitable fillers include modified or natural clays,modified or unmodified synthetic clays, talc glass fiber, powderedglass, modified or natural silica, calcium carbonate, mica, paper, woodchips, and combinations thereof.

In some embodiments, the chassis 1034 can include one or more semi-rigidplate components, such as carbon-fiber plates, polymeric (e.g.,polyamide-based) plates, and the like. In further alternativeembodiments, the chassis 1034 can be omitted and the airsole 1036 can bedirectly secured to the upper 1026.

As shown in FIGS. 1 and 2 , the outsole 1032 can have a geometry thatmatches the geometry of airsole 1036 and is configured to provide aground-engaging surface of the footwear 1010. For example, the outsole1032 can be provided as a polymeric component that is overmolded onto,adhered to, or otherwise secured to the airsole 1036 to provideincreased durability, puncture resistance, and/or abrasion resistance tothe airsole 1036 in the ground-facing direction. Examples of suitablematerials for the outsole 1032 include those capable of bonding to theairsole 1036 directly and/or with adhesives, and that preferably exhibitabrasion resistance and/or puncture resistance, such as polyurethanes,thermoplastic polyurethanes, polyether block amines, vulcanized rubbers,and combinations thereof.

The airsole 1036 is an example airbag for use with the footwear 1010 andincorporates the multi-layered film of the present disclosure. Asbriefly noted above, the multi-layered film exhibits an increasedbalance between durability and flexibility, while also retaining goodgas-barrier properties. As such, airsoles incorporating themulti-layered film can have a broader range of unique and advancedthree-dimensional geometries than those achievable with current barrierfilms.

For example, the airsole 1036 can include one or more protruding and/orbulbous portions, such as a heel portion 1038 at the heel region 1016,medial portions 1040 a, 1040 b, and 1040 c at the medial side 1022,and/or lateral portions 1042 a, 1042 b, and 1042 c at the lateral side1024. These protruding portions, particularly heel portion 1038, canpotentially be subjected to high stress loads from flexing and releaseduring each foot strike due to their extreme geometries, potentiallyresulting in significant flexing deformation of the multi-layered filmand the barrier layers within. This is best illustrated in FIG. 3 ,which shows the portions 1038; 1040 a, 1040 b, and 1040 c; and 1042 a,1042 b, and 1042 c of the airsole 1036 extending beyond a top-down,cross-sectional footprint of the chassis 1034 of the midsole 1030. Ascan be appreciated, during each foot strike, the downward pressureapplied to the airsole 1036 by the wearer's body weight and transferredthrough the upper 1026 and the chassis 1034 can generate high stressloads on the protruding portions 1038; 1040 a, 1040 b, and 1040 c; and1042 a, 1042 b, and 1042 c. These high stress loads resulting fromflexing and release of the multi-layered film can be particularly highat the heel portion 1038 due to heel-striking during walking andrunning. Furthermore, these high stress loads are compounded over timethrough repeated flexing and release of the multi-layered film of theairsole 1036, which can occur with each foot strike.

In any of the above aspects, flexing and release stress loads applied tothe multi-layered film of the airsole 1036 can exceed the performancetolerances of currently-known barrier films over repeated foot strikesin footwear applications, which can produce visible crazing or hazingeffects in the barrier films. While these crazing and hazing effects donot noticeably affect the performance of the barrier films (e.g., gasretention), they can detract from the aesthetics of the airsoles, whichmay be an undesirable effect for many consumers. The multi-layered filmof the present disclosure, however, can withstand higher repeated stressloads compared to current barrier films used in footwear applicationswhile exhibiting reduced or no visually observable cracking, crazing, orhazing and, further, retaining good gas-barrier properties. Thegas-barrier layers of the core region(s) in the disclosed multi-layeredfilm may, in particular, have an average layer thickness of less thanabout 2 micrometers, optionally an average layer thickness of less thanor equal to 0.75 micrometers, or less than about 0.5 micrometers, suchas an average layer thickness in a range of from about 0.01 micrometersto about 0.75 micrometers, optionally in a range of from about 0.01micrometers to about 0.5 micrometers; and have increased flexibilityand/or elastic properties compared to currently-known barrier films,allowing the multi-layered film of the present disclosure to undergorepeated flexing-release cycles substantially without losing gas-barrierproperties and without the appearance of crazing, hazing, or the like.Further in this aspect, these superior properties allow for thedisclosed airsoles 1036 to have a longer useful lifetime without anappreciable change in gas transmission rate.

Furthermore, while particularly beneficial for use with airbags havingmore extreme geometries (e.g., airsole 1036 with uncompressed height1046), the multi-layered film of the present disclosure can be used as asuitable replacement in any current gas-barrier applications thatincorporate multi-layered films (e.g., microlayer films). For example,in footwear applications, the multi-layered film can be incorporatedinto airsoles having any suitable geometry, such as those disclosed inU.S. Pat. Nos. 10,149,513, 11,019,880, and 11,019,881 and U.S. PatentApplication Publication Nos. 2019/0231027, 2020/0205514, 2021/0145119,and 2021/0195996. This allows the same multi-layered film to beinterchangeably used as feedstock for multiple different airsolegeometries, thereby increasing manufacturing efficiency, reducing rawmaterial waste, and reducing manufacturing carbon impact.

As shown in FIG. 4 , multi-layered film 1076 is an example multi-layeredfilm of the present disclosure, such as for use in the airsole 1036. Insome aspects, the articles disclosed herein can comprise multiple layersas illustrated, for example, in FIG. 4 . In this exemplary embodiment,the article is a sheet comprising gas-barrier layers and includes twostructural layers, 2200 a having a thickness 2180 a and 2200 b having athickness 2180 b and a core region or film 2160 having a thickness 2140.In one aspect, the article can be two-sided. Further in this aspect, atwo-sided article can include a symmetrical arrangement of layers onboth sides of core region 2160. Suitable examples of thicknesses 2180 aand 2180 b range from about 900 micrometers to about 1990 micrometers,or from about 900 micrometers to about 1400 micrometers, or from about1400 micrometers to about 1990 micrometers. Suitable examples ofthickness 2140 range from about 125 micrometers to about 200micrometers, or from about 125 micrometers to about 175 micrometers, orfrom about 150 micrometers to about 200 micrometers.

In one such aspect in accordance with the example of FIG. 4 , structurallayers 2200 a and 2200 b can comprise or consist essentially of astructural layer material. In such an aspect, the core region 2160 cancomprise or consist essentially of a multi-layered film comprisinggas-barrier layers as disclosed herein.

In any of these aspects, structural layer 2200 a can have a firstsurface 2200 a′ and a second surface 2200 a″, while structural layer2200 b can have a first surface 2200 b′ and a second surface 2200 b″. Inanother aspect, the core region 2160 can have a first surface 2160 a anda second surface 2160 b. In some aspects, the second surface 2200 a″ ofthe structural layer 2200 a and the first surface 2160 a of the coreregion 2160 can be adjacent to one another or otherwise in contact withone another. In one aspect, the second surface 2160 b of the core region2160 and the second surface 2200 b″ of the structural layer 2200 b canbe adjacent to one another or otherwise in contact with one another. Insome aspects, first surface 2200 a′ of structural layer 2200 a and/orfirst surface 2200 b′ of structural layer 2200 b can independentlyoptionally be an outer surface of an article incorporating themulti-layered film disclosed herein. In any of these aspects, structurallayer 2200 a and structural layer 2200 can be made from the samematerial or from different materials and can have the same or differentthicknesses.

In one aspect, provided herein are articles comprising the multi-layeredfilms disclosed herein, the articles including:

-   -   a first cap layer comprising or consisting essentially of a        first cap layer material, the first cap layer including a first        cap layer outer surface defining a first outer surface of the        multi-layered film, a first cap inner layer surface opposing the        first cap layer outer surface, a first cap layer thickness        extending from the first cap layer inner surface to the first        cap layer outer surface, wherein the first cap layer outer        surface defines a first exterior surface of the article;    -   a second cap layer comprising or consisting essentially of a        second cap layer material, the second cap layer including a        second cap layer outer surface defining a second outer surface        of the multi-layered film, a second cap layer inner surface        opposing the second cap layer outer surface, a second cap layer        thickness extending from the second cap layer inner surface to        the second cap layer outer surface, optionally wherein the        second cap layer outer surface defines a second exterior surface        of the article; and    -   one or more core regions, wherein each of the one or more core        regions comprises or consists essentially of the multi-layered        film, each of the one or more core regions including a core        region first surface, a core region second surface, and a core        region thickness extending from the core region first surface to        the core region second surface, wherein each of the one or more        core regions is positioned between the first cap layer inner        surface and the second cap layer inner surface.

In another aspect, the first cap layer material and the second cap layermaterial are substantially the same. In an alternative aspect, the firstcap layer material and the second cap layer material are different. Insome aspects, the first cap layer inner surface is in contact with thecore region first surface, or the second cap layer inner surface is incontact with the core region second surface, or both.

In one aspect, the gas-barrier material comprises or consistsessentially of a nitrogen barrier material. In a further aspect, thegas-barrier material comprises or consists essentially of one or moregas-barrier polymers. Further in this aspect, the gas-barrier materialcan comprise a gas-barrier polymeric component consisting of allpolymers present in the gas-barrier material. In another aspect, the oneor more gas-barrier polymers comprise or consist essentially of one ormore thermoplastic vinylidene chloride polymers, one or morethermoplastic acrylonitrile polymers or copolymers, one or morethermoplastic polyamides, one or more thermoplastic epoxy resins, one ormore thermoplastic amine polymers or copolymers, or one or morethermoplastic polyolefin homopolymers or copolymers. In one aspect, theone or more thermoplastic polyolefin homopolymers or copolymers compriseor consist essentially of one or more thermoplastic polyethylenecopolymers, or comprise or consist essentially of one or morethermoplastic ethylene-vinyl alcohol copolymers. In one aspect, the oneor more ethylene-vinyl alcohol copolymers include from about 28 molepercent to about 44 mole percent ethylene content, or from about 32 molepercent to about 44 mole percent ethylene content.

In another aspect, the elastomeric material comprises or consistsessentially of one or more thermoplastic elastomeric polymers, andfurther comprises an elastomeric polymeric component consisting of allpolymers present in the elastomeric material. In another aspect, the oneor more thermoplastic elastomeric polymers comprise or consistessentially of one or more thermoplastic elastomeric polyolefinhomopolymers or copolymers, one or more thermoplastic elastomericpolyamide homopolymers or copolymers, one or more thermoplasticelastomeric polyester homopolymers or copolymers, one or morethermoplastic elastomeric polyurethane homopolymers or copolymers, oneor more thermoplastic elastomeric styrenic homopolymers or copolymers,or any combination thereof.

In further aspects, the one or more styrenic homopolymers or copolymerscan include one or more styrenic block copolymers, such as acrylonitrilebutadiene styrene block copolymers, styrene acrylonitrile blockcopolymers, styrene ethylene butylene styrene block copolymers, styreneethylene butadiene styrene block copolymers, styrene ethylene propylenestyrene block copolymers, styrene butadiene styrene block copolymers,and combinations thereof.

In an aspect, the elastomeric material comprises or consists essentiallyof one or more thermoplastic elastomeric polyurethane homopolymers orcopolymers, optionally wherein the elastomeric material comprises orconsists essentially of one or more polydiene polyol-based thermoplasticelastomeric polyurethane homopolymers or copolymers.

In some aspects, the one or more thermoplastic elastomeric polyurethanehomopolymers or copolymers comprise a plurality of first segmentsderived from one or more polyols and a plurality of segments derivedfrom a diisocyanate. In another aspect, the one or more thermoplasticelastomeric polyurethane homopolymers or copolymers is a polymerizationproduct of a diisocyanate with one or more polyols.

In another aspect, the thermoplastic elastomeric polyurethanehomopolymer or copolymer comprises or consists essentially of one ormore polydiene polyol-based thermoplastic elastomeric polyurethanehomopolymers or copolymers, wherein the polyol comprises or consistsessentially of a polybutadiene polyol, a polyisoprene polyol, apartially or fully hydrogenated derivative of a polybutadiene polyol orof a polyisoprene polyol, or any combination thereof.

In another aspect, the one or more polyols comprise or consistessentially of a polyester polyol, a polyether polyol, a polycarbonatepolyol, a polycaprolactone polyether, or any combination thereof.

In still another aspect, the diisocyanate comprises or consistsessentially of an aliphatic diisocyanate, an aromatic diisocyanate, orany combination thereof. In one aspect, the aliphatic diisocyanatecomprises or consists essentially of hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), butylenediisocyanate (BDI),bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylenediisocyanate (TMDI), bisisocyanatomethylcyclohexane,bisisochanatomethyltricyclodecane, norbornane diisocyanate (NDI),cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexhylmethane diisocyanate(H12MDI), diisocyanatododecane, lysine diisocyanate, or any combinationthereof. In another aspect, the aromatic diisocyanate comprises orconsists essentially of toluene diisocyanate (TDI), TDI adducts withtrimethylolpropane (TMP), methylene diphenyl diisocyanate (MDI), xylenediisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI),hydrogenated xylene diisocyanate (HXDI), naphthalene 1,5-diisocyanate(NDI), 1,5-tetrahydronaphthalene diisocyanate, para-phenylenediisocyanate (PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI),4,4′-dibenzyl diisocyanate (DBDI), 4-chloro-1,3-phenylene diisocyanate,or any combination thereof.

In an aspect, in the multi-layered films, the gas-barrier material canhave a melt flow index of from about 5 to about 7 grams per 10 minutesat 190 degrees Celsius when using a weight of 2.16 kilograms. In anotheraspect, the elastomeric material can have a melt flow index of fromabout 20 to about 30 grams per 10 minutes at 190 degrees Celsius whenusing a weight of 2.16 kilograms. In any of these aspects, in themulti-layered films, the melt flow index of the gas-barrier material canbe from about 80 percent to about 120 percent of the melt flow index ofthe elastomeric material, or from about 90 percent to about 110 percentof the melt flow index of the elastomeric material, from about 95percent to about 105 percent of the melt flow index of the elastomericmaterial, or can be substantially the same as the melt flow index of theelastomeric material, when the melt flow index is measured in cubiccentimeters per 10 minutes at 190 degrees Celsius when using a weight of2.16 kilograms.

In one aspect, the gas-barrier material can have a melting temperatureof from about 165 degrees Celsius to about 183 degrees Celsius, while inanother aspect, the elastomeric material can have a melting temperatureof from about 155 degrees Celsius to about 165 degrees Celsius. In anyof these aspects, the melting temperature of the gas-barrier material iswithin about 10 degrees Celsius of the melting temperature of theelastomeric material, optionally within about 8 degrees Celsius of themelting temperature of the elastomeric material, or within about 5degrees Celsius of the melting temperature of the elastomeric material.

In any of these aspects, without wishing to be bound by theory, thingas-barrier layers alternating with elastomeric layers as disclosedherein can improve the flexibility tolerances of the core region ormulti-layered film without compromising durability or gas-barrierproperties. Further in this aspect, the disclosed multi-layered filmsallow for the production of articles incorporating the multi-layeredfilms, wherein the articles can incorporate extreme geometries withoutexhibiting cracking, crazing, hazing, or loss of gas-barrier propertiesover time.

In some aspects, the multi-layered films disclosed herein furthercomprise a blended material, wherein the blended material comprises orconsists essentially of a blend of one or more additional thermoplasticelastomers and a second material, optionally wherein the second materialcomprises or consists essentially of one or more second polymers,optionally wherein the one or more second polymers comprise or consistessentially of one or more second thermoplastics.

In an aspect, the one or more second thermoplastics can comprise one ormore thermoplastic polyolefin homopolymers, one or more thermoplasticpolyamide homopolymers or copolymers, one or more thermoplasticpolyester homopolymers or copolymers, one or more thermoplasticpolyurethane homopolymers or copolymers, one or more thermoplasticstyrenic homopolymers or copolymers, or any combination thereof.

In further aspects, the one or more styrenic homopolymers or copolymerscan include one or more styrenic block copolymers, such as acrylonitrilebutadiene styrene block copolymers, styrene acrylonitrile blockcopolymers, styrene ethylene butylene styrene block copolymers, styreneethylene butadiene styrene block copolymers, styrene ethylene propylenestyrene block copolymers, styrene butadiene styrene block copolymers,and combinations thereof.

In another aspect, the one or more second thermoplastics can comprise orconsist essentially of thermoplastic polypropylene homopolymers orcopolymers, thermoplastic polyethylene homopolymers or copolymers,thermoplastic polybutylene homopolymers or copolymers, or anycombination thereof.

In some aspects, the one or more second thermoplastics comprise orconsist essentially of one or more thermoplastic polyethylenecopolymers. In another aspect, the one or more second thermoplasticscomprise or consist essentially of one or more thermoplasticethylene-vinyl alcohol copolymers. In one aspect, a polymeric componentof the blended material consists of one or more additional thermoplasticelastomeric polyurethane homopolymers or copolymers, and one or moresecond thermoplastic ethylene-vinyl alcohol copolymers. In analternative aspect, the polymeric component of the thermoplasticelastomeric material consists of one or more additional thermoplasticelastomeric polyester-polyurethane copolymers and one or more secondthermoplastic ethylene-vinyl alcohol copolymers. In some aspects, theblended material comprises one or more recycled additional thermoplasticelastomers, or one or more recycled second thermoplastics, or both.

In some aspects, the blended material is a phase-separated blend of theone or more additional thermoplastic elastomers and the one or moresecond thermoplastics. In some aspects, the phase-separated blendincludes one or more phase-separated regions including interfacesbetween the one or more additional thermoplastic elastomers and the oneor more second thermoplastics. In some aspects, the blend comprisesabout 95 percent by weight of the one or more second thermoplastics andabout 5 percent by weight of the one or more second thermoplastics basedon a total weight of the blend.

As used herein, the term recycled material may refer to a polymericmaterial which has previously been extruded into a film, and may havebeen previously thermoformed into a bladder, before being shredded orground and re-extruded into a film. Optionally, therefore, the thermalhistory of a material may provide evidence that it is a recycledmaterial, rather than a virgin material. Optionally, a recycledmaterial, or a recycled polymeric material, may comprise up to 10percent of a gas-barrier polymeric material on a weight basis, as it mayhave been recycled by grinding or shredding a multi-layered film thatincluded a gas-barrier material. In an aspect, the disclosedmulti-layered films further comprise a recycled material comprising oneor more recycled polymers, optionally wherein the one or more recycledpolymers comprise one or more recycled thermoplastics, optionallywherein the one or more recycled thermoplastics comprise one or morerecycled thermoplastic elastomers; optionally wherein the recycledmaterial comprises a recycled material polymeric component consisting ofone or more recycled thermoplastics, optionally wherein the recycledmaterial polymeric component comprises or consists essentially of one ormore recycled thermoplastic elastomers.

In another aspect, the recycled material can comprise one or morerecycled thermoplastic elastomers, and optionally the one or morerecycled thermoplastic elastomers comprise one or more regroundthermoplastic elastomers, optionally wherein the one or more recycled orreground thermoplastic elastomers includes a thermoplastic elastomericmaterial as disclosed herein.

In some aspects, the recycled material further comprises one or morerecycled second thermoplastics, and the one or more recycled secondthermoplastics optionally comprise one or more reground secondthermoplastics, optionally wherein the one or more recycled or regroundsecond thermoplastics include a thermoplastic as disclosed herein.

In one aspect, the recycled material comprises one or more recycled orreground thermoplastic polyurethane elastomers or one or more recycledor reground thermoplastic ethylene-vinyl alcohol copolymers or both. Inan aspect, the recycled material comprises a blend of the one or morerecycled or reground thermoplastic elastomers and one or more secondthermoplastics, or comprises a blend of one or more thermoplasticelastomers and one or more recycled thermoplastics or one or morerecycled thermoplastics, optionally wherein the blend is aphase-separated blend, and optionally wherein the phase-separated blendcomprises one or more interfaces between the one or more recycledthermoplastic elastomers and the one or more second thermoplastics.

In another aspect, in the multi-layered films, the recycled materialcomprises about 99 percent to about 90 percent by weight of the one ormore recycled thermoplastic elastomers and about 1 percent to about 10percent by weight of the one or more second thermoplastics based on atotal weight of the recycled material, optionally wherein the recycledmaterial comprises about 99 percent to about 93 percent by weight of theone or more recycled thermoplastic elastomers and about 1 percent toabout 7 percent by weight of the one or more second thermoplastics, orabout 99 percent to about 95 percent by weight of the one or morerecycled thermoplastic elastomers and about 1 percent to about 5 percentby weight of the one or more second thermoplastic elastomers.

In an aspect, the recycled material comprises about 99 percent to about50 percent by weight of recycled or reground polymers based on a totalweight of recycled material, or from about 99 percent to about 75percent by weight of recycled or reground polymers.

In some aspects, the recycled material further comprises one or morevirgin first thermoplastic elastomers, optionally wherein the one ormore virgin thermoplastic elastomers includes one or more virginthermoplastic polyurethane elastomers.

In one aspect, the multi-layered film further comprises one or more tielayers, each of the one or more tie layers individually comprising orconsisting essentially of a tie material, wherein the one or more tielayers increase a bond strength between two adjacent layers. In someaspects, the tie material of each of the one or more tie layersindependently comprises or consists essentially of a polyurethane, apolyacrylate, an ethylene-acrylate copolymer, a maleic anhydride graftedpolyolefin, or any combination thereof, and optionally the tie materialcomprises or consists essentially of a blended material or a recycledmaterial as disclosed herein. In another aspect, the tie layer materialof the one or more tie layers independently comprises or consistsessentially of one or more thermoplastic polyurethane elastomerichomopolymers or copolymers, optionally wherein the one or more tielayers comprise or consist essentially of polydiene polyol-basedthermoplastic polyurethane.

In one aspect, in the multi-layered films, the elastomeric material canbe a first elastomeric material, and the multi-layered films furtherinclude a second elastomeric material, and the formed multi-layered filmfurther comprises a first structural layer secured to a first side ofone of the one or more core regions, wherein the first structural layercomprises the second elastomeric material and has an average thicknessranging from about 900 micrometers to about 1990 micrometers, optionallyfrom about 900 to about 1500 micrometers, from about 1500 to about 1990micrometers, from about 1200 to about 1800 micrometers, or from about1000 to about 1400 micrometers.

In another aspect, the multi-layered films further comprise one or morestructural layers, each of the one or more structural layersindependently comprising or consisting essentially of a structural layermaterial, optionally wherein the structural layer material comprises orconsists essentially of a blended material or a recycled material asdescribed herein. In some aspects, the structural layer material of theone or more structural layers independently comprises or consistsessentially of a polydiene polyol-based thermoplastic polyurethane.

In still another aspect, the multi-layered films can comprise one ormore cap layers, wherein the one or more cap layers comprise or consistessentially of a cap layer material, optionally wherein the cap layermaterial comprises or consists essentially of a blended material or arecycled material as disclosed herein. In some aspects, the cap layermaterial of the one or more cap layers comprises or consists essentiallyof a polyurethane, a polyacrylate, an ethylene-acrylate copolymer, amaleic anhydride grafted polyolefin, or any combination thereof. Inanother aspect, the cap layer material of the one or more cap layerscomprises or consists essentially of a thermoplastic polyurethane,optionally a polydiene polyol-based thermoplastic polyurethane.

In some aspects, at least one of the one or more tie layers ispositioned between one of the one or more structural layers and one ofthe one or more core regions. In another aspect, at least one of the oneor more structural layers is positioned between one of the one or moretie layers and one of the one or more cap layers. In another aspect, themulti-layered film can be a coextruded layered sheet or a laminatedlayered sheet.

In one aspect, disclosed herein is a multi-layered film comprising afirst cap layer, a first structural layer, a first tie layer, a coreregion, a second tie layer, a second structural layer, and a second caplayer, wherein a first cap layer inner surface contacts a first surfaceof the first structural layer, a second surface of the first structurallayer contacts a first surface of the first tie layer, a second surfaceof the first tie layer contacts a first surface of the core region, asecond surface of the core region contacts a first surface of the secondtie layer, a second surface of the second tie layer contacts a firstsurface of the second structural layer, and a second surface of thesecond structural layer contacts an inner layer of the second cap layer.

In an alternative aspect, the disclosed multi-layered films have astructure of A-B-C-B-A, wherein A represents a structural layer, Brepresents a tie layer, and C represents a core region. In anotheraspect, the disclosed multi-layered films have a structure ofD-A-B-C-B-A-D, wherein A represents a structural layer, B represents atie layer, C represents a core region, and D represents a cap layer.

In an aspect, in any of the disclosed multi-layered films, each of theone or more core regions can have a gas transmission rate of from about0.3 to about 1.9 cubic centimeters per square meter per day for nitrogenmeasured at 23 degrees Celsius and 0 percent relative humidity,optionally for a structure having a thickness of from about 72micrometers to about 320 micrometers, optionally wherein each of the oneor more core regions can have a gas transmission rate of from about 0.3to about 1.9 cubic centimeters per square meter per day for nitrogenmeasured at 23 degrees Celsius and 0 percent relative humidity,optionally for a structure having a thickness of from about 72micrometers to about 320 micrometers

In any of these aspects, the multi-layered film further comprises one ormore protective layers, each of the one or more protective layersindividually comprising or consisting essentially of a protectivematerial, wherein each of the one or more protective layers is adjacentto a core region and has a protective layer thickness, wherein acombination of the one or more protective layers and the adjacent coreregion has a minimum radius of curvature which is greater than a minimumradius of curvature which causes cracking of the core region, or of oneor more individual layers within the core region.

Turning to FIG. 5 , in one aspect, disclosed herein are multi-layeredfilms, the multi-layered films comprising one or more core regions 2160,wherein each of the one or more core regions comprises a plurality oflayers, the plurality of layers comprising gas-barrier layers 3020comprising at least one gas-barrier material alternating withelastomeric layers 3010 comprising at least one elastomeric material;wherein each of the gas-barrier layers has a thickness 3021 of fromabout 0.5 micrometers to about 2 micrometers thick, or from about 0.5micrometers to about 1 micrometer thick; or optionally less than orequal to 0.75 micrometers thick, or less than or equal to 0.5micrometers thick, or in a range of from about 0.01 micrometers to about0.75 micrometers thick, optionally in a range of from about 0.01micrometers to about 0.5 micrometers thick; and wherein each of theelastomeric layers has a thickness 3011 of from about 2 micrometers toabout 8 micrometers thick, or from about 2 micrometers to about 4micrometers thick. In some aspects core region 2160 is adjacent toanother layer 3030 such as, for example, a tie layer, a structurallayer, or a cap layer.

In another aspect, each of the one or more core regions comprises atleast 50 layers, or from about 50 to about 100 layers, from about 50 toabout 90 layers, from about 50 to about 80 layers, from about 50 toabout 70 layers, from about 60 to about 100 layers, from about 60 toabout 90 layers, or from about 60 to about 80 layers. In one aspect,each of the one or more core regions has an average total thickness lessthan 200 micrometers, optionally from about 125 micrometers to about 200micrometers, or from about 125 micrometers to about 175 micrometers, orfrom about 150 micrometers to about 200 micrometers.

Referring now to FIG. 6A, in an alternative aspect, a sheet ormulti-layered film can incorporate single structural layer 2200 acomprising a structural material and core region 2160 comprisinggas-barrier layers.

In some aspects, the articles disclosed herein can comprise multiplelayers as illustrated, for example, in FIG. 6B. In this exemplaryembodiment, the article is a sheet comprising gas-barrier layers andincludes a two cap layers, 2120 a having a thickness 2100 a and 2120 bhaving a thickness 2100 b, two structural layers, 2200 a having athickness 2180 a and 2200 b having a thickness 2180 b, and a core region2160 having a thickness 2140. Suitable examples of thicknesses 2180 aand 2180 b range from about 900 micrometers to about 1990 micrometers,or from about 900 micrometers to about 1400 micrometers, or from about1400 micrometers to about 1990 micrometers. Suitable examples ofthickness 2140 range from about 125 micrometers to about 200micrometers, or from about 125 micrometers to about 175 micrometers, orfrom about 150 micrometers to about 200 micrometers. Suitable examplesof thicknesses 2100 a and 2100 b range from about 5 micrometers to about25 micrometers. In one aspect, the article can be two-sided. Further inthis aspect, a two-sided article can include a symmetrical arrangementof layers on both sides of core region 2160.

In one such aspect in accordance with the example of FIG. 6B, cap layers2120 a and 2120 b can comprise or consist essentially of a cap layermaterial. In such an aspect, structural layers 2200 a and 2200 b canalso comprise or consist essentially of a structural layer material, orcan comprise or consist essentially of a barrier material. In such anaspect, the core region 2160 can comprise or consist essentially of amulti-layered film as disclosed herein.

In any of these aspects, the cap layer 2120 a can have a first surface2120 a′ and a second surface 2120 a″, while the cap layer 2120 b canhave a first surface 2120 b′ and a second surface 2120 b″. In anotheraspect, the structural layer 2200 a can have a first surface 2200 a′ anda second surface 2200 a″, while the core region 2200 b can have a firstsurface 2200 b′ and a second surface 2200 b″. In still another aspect,the core region 2160 can have a first surface 2160 a and a secondsurface 2160 b. In some aspects, the second surface 2120 a″ of the caplayer 2120 a and the first surface 2200 a′ of the structural layer 2200a can be adjacent to one another or otherwise in contact with oneanother. In a further aspect, the second surface 2200 a″ of thestructural layer 2200 a and the first surface 2160 a of the core regionand the second surface 2200 a″ of the structural layer 2200 a can beadjacent to one another or otherwise in contact with one another. In oneaspect, the second surface 2160 b of the core region 2160 and the secondsurface 2200 b″ of the structural layer 2200 b can be adjacent to oneanother or otherwise in contact with one another. In still anotheraspect, the first surface 2200 b′ of the structural layer 2200 b and thesecond surface 2120 b″ of the cap layer 2120 b can be adjacent to oneanother or otherwise in contact with one another. In some aspects, firstsurface 2120 a′ of cap layer 2120 a and/or first surface 2120 b′ of caplayer 2120 b can independently optionally be an outer surface of anarticle incorporating the multi-layered film disclosed herein. In any ofthese aspects, structural layer 2200 a and structural layer 2200 b canbe made from the same material or from different materials and can havethe same or different thicknesses. In another aspect, cap layer 2120 aand cap layer 2120 b can be made from the same material or fromdifferent materials and can have the same or different thicknesses.

In another aspect, the article can be configured as a series of four ormore layers including one or more structural layers, each of the one ormore structural layers comprising a structural layer material andincluding a structural layer first surface, a structural layer secondsurface opposing the structural layer first surface, and a structurallayer thickness extending from the structural layer first surface to thestructural layer second surface;

-   -   optionally wherein at least one of the one or more structural        layers is positioned between the first cap layer and the core        region, or between the second cap layer and the core region; or    -   optionally wherein the one or more structural layers comprise        two or more structural layers, and at least a first one of the        two or more structural layers is positioned between an inner        surface of a first cap layer and the first surface of a core        region, and at least a second one of the two or more structural        layers is positioned between a second surface of a core region        and the inner surface of the second cap layer.

In another aspect, a first surface of a first one of the structurallayers is in contact with the inner surface of the first cap layer, andthe second surface of the first one of the structural layers is incontact with a first surface of one of the one or more core regions, orthe first surface of a second one of the one or more structural layersis in contact with the second surface of one of the one or more coreregions, and the second surface of the second one of the structurallayers is in contact with an inner surface of the second cap layer, orboth.

In one aspect, the one or more structural layers comprise or consistessentially of the blended material or the recycled material asdisclosed herein.

Referring now to FIG. 6C, in an alternative aspect, a sheet ormulti-layered film can incorporate single structural layer 2200 acomprising a structural material, single cap layer 2120 a comprising acap layer material, and core region 2160 comprising gas-barrier layers.

In some aspects, the articles disclosed herein can comprise multiplelayers as illustrated, for example, in FIG. 6D. In this exemplaryembodiment, the article is a sheet comprising gas-barrier layers andincludes two cap layers, specifically cap layer 2120 a (having athickness 2100 a), cap layer 2120 b (having a thickness 2100 b); twostructural layers, specifically structural layer (2200 a having athickness 2180 a), structural layer 2200 b (having a thickness 2180 b);two tie layers, specifically tie layer 2240 a (having a thickness 2220a) and tie layer 2240 b (having a thickness 2220 b); and a core regionor layer 2160 (having a thickness 2140). Suitable examples ofthicknesses 2180 a and 2180 b range from about 900 micrometers to about1990 micrometers, or from about 900 micrometers to about 1400micrometers, or from about 1400 micrometers to about 1990 micrometers.Suitable examples of thickness 2140 range from about 125 micrometers toabout 200 micrometers, or from about 125 micrometers to about 175micrometers, or from about 150 micrometers to about 200 micrometers.Suitable examples of thicknesses 2100 a and 2100 b range from about 5micrometers to about 25 micrometers. Suitable examples of thicknesses2220 a and 2220 b range from about 5 micrometers to about 20micrometers. In one aspect, the article can be two-sided. Further inthis aspect, a two-sided article can include a symmetrical arrangementof layers on both sides of core region 2160.

In one such aspect in accordance with the example of FIG. 6D, cap layers2120 a and 2120 b can comprise or consist essentially of a cap layermaterial. In such an aspect, structural layers 2200 a and 2200 b canalso comprise or consist essentially of a structural layer material, orcan comprise or consist essentially of a barrier material. In such anaspect, the tie layers 2240 a and 2240 b can comprise or consistessentially of a tie material, or can comprise or consist essentially ofa barrier material. In such an aspect, the core region 2160 can compriseor consist essentially of a multi-layered film as disclosed herein.

In any of these aspects, the cap layer 2120 a can have a first surface2120 a′ and a second surface 2120 a″, while the cap layer 2120 b canhave a first surface 2120 b′ and a second surface 2120 b″. In anotheraspect, the structural layer 2200 a can have a first surface 2200 a′ anda second surface 2200 a″, while the core region 2200 b can have a firstsurface 2200 b′ and a second surface 2200 b″. In still another aspect,the tie layer 2240 a can have a first surface 2240 a′ and a secondsurface 2240 a″, while the tie layer 2240 b can have a first surface2240 b′ and a second surface 2240 b″. In still another aspect, the coreregion 2160 can have a first surface 2160 a and a second surface 2160 b.In some aspects, the second surface 2120 a″ of the cap layer 2120 a andthe first surface 2200 a′ of the structural layer 2200 a can be adjacentto one another or otherwise in contact with one another. In a furtheraspect, the second surface 2200 a″ of the structural layer 2200 a andthe first surface 2240 a′ of the tie layer 2240 a can be adjacent to oneanother or otherwise in contact with one another. In a still furtheraspect, the first surface 2160 a of the core region and the secondsurface 2240 a″ of the tie layer 2240 a can be adjacent to one anotheror otherwise in contact with one another. In one aspect, the secondsurface 2160 b of the core region 2160 and the second surface 2240 b″ ofthe tie layer 2240 b can be adjacent to one another or otherwise incontact with one another. In another aspect, the first surface 2240 b′of the tie layer 2240 b and the second surface 2200 b″ of the structurallayer 2200 b can be adjacent to one another or otherwise in contact withone another. In still another aspect, the first surface 2200 b′ of thestructural layer 2200 b and the second surface 2120 b″ of the cap layer2120 b can be adjacent to one another or otherwise in contact with oneanother. In some aspects, first surface 2120 a′ of cap layer 2120 aand/or first surface 2120 b′ of cap layer 2120 b can independentlyoptionally be an outer surface of an article incorporating themulti-layered film disclosed herein. In any of these aspects, structurallayer 2200 a and structural layer 2200 b can be made from the samematerial or from different materials and can have the same or differentthicknesses. In a further aspect, cap layer 2120 a and cap layer 2120 bcan be made from the same material or from different materials and canhave the same or different thicknesses. In a still further aspect, tielayer 2240 a and tie layer 2240 b can be made from the same material orfrom different materials and can have the same or different thicknesses.

Referring now to FIG. 6E, in an alternative aspect, a sheet ormulti-layered film can incorporate single structural layer 2200 acomprising a structural material, single cap layer 2120 a comprising acap layer material, single tie layer 2240 a comprising a tie layermaterial, and core region 2160 comprising gas-barrier layers.

In an aspect, the article can be configured as a series of five or morelayers including one or more tie layers, each of the one or more tielayers including a tie layer first surface, a tie layer second surfaceopposing the tie layer first surface, and a tie layer thicknessextending from the tie layer first surface to the tie layer secondsurface;

-   -   optionally wherein at least one of the one or more tie layers is        positioned between one of the one or more structural layers and        one of the one or more core regions, or between the first cap        layer and one of the one or more structural layers, or between        the second cap layer and one of the one or more structural        layers, or any combination thereof; or    -   optionally wherein the one or more tie layers comprise two or        more tie layers, and at least a first one of the two or more tie        layers is positioned between a second surface of a first        structural layer and a first layer of a core region, and at        least a second one of the two or more tie layers is positioned        between a second surface of a core region and a first surface of        a structural layer.

In one aspect, a first surface of a first one of the one or more tielayers is in contact with a second surface of a first one of the one ormore structural layers, and the second surface of the first one of theone or more tie layers is in contact with a first surface of a coreregion, or wherein a first surface of a second one of the one or moretie layers is in contact with a second surface of one of the one or morecore regions, and the second surface of the second one of the one ormore tie layers is in contact with a first surface of a second one ofthe one or more structural layers, or both.

In an aspect, the article comprises the first cap layer, a firststructural layer, a first tie layer, a core region, a second tie layer,a second structural layer, and the second cap layer, wherein the firstcap layer inner surface contacts the first surface of the firststructural layer, the second surface of the first structural layercontacts the first surface of the first tie layer, the second surface ofthe first tie layer contacts the first surface of the core region, thesecond surface of the core region contacts the first surface of thesecond tie layer, the second surface of the second tie layer contactsthe first surface of the second structural layer, and the second surfaceof the second structural layer contacts the inner layer of the secondcap layer, and optionally the core region comprises one or more coreregions, or comprises a plurality of microlayers.

One or both of the sheets comprising gas-barrier layers as shown inFIGS. 4 and 6A-6E can independently be transparent, translucent, and/oropaque. As used herein, the term “transparent” for a barrier layerand/or a bladder means that light passes through the barrier layer insubstantially straight lines and a viewer can see through the barrierlayer. In comparison, for an opaque barrier layer, light does not passthrough the barrier layer and one cannot see clearly through the barrierlayer at all. A translucent barrier layer falls between a transparentbarrier layer and an opaque barrier layer, in that light passes througha translucent layer but some of the light is scattered so that a viewercannot see clearly through the layer.

The airsole 1036 can be produced from the sheets comprising gas-barrierlayers as shown in FIGS. 4 and 6A-6E using any suitable technique, suchas thermoforming (e.g. vacuum thermoforming), blow molding, extrusion,injection molding, vacuum molding, rotary molding, transfer molding,pressure forming, heat sealing, casting, low-pressure casting, spincasting, reaction injection molding, radio frequency (RF) welding, andthe like. In an aspect, the sheets comprising gas-barrier layers asshown in FIGS. 4 and 6A-6E can be produced by co-extrusion followed byvacuum thermoforming to form the profile of the airsole 1036 which canoptionally include one or more valves (e.g., one way valves) that allowsthe airsole 1036 to be filled with the fluid (e.g., gas).

In any of these aspects, the multi-layered films and articles producedtherefrom are suitable for use in mass-market products including, butnot limited to, articles of footwear, articles of sporting equipment,articles of athletic apparel, personal protective equipment, and thelike.

In an aspect, the multi-layered films and articles formed therefrom caninclude one or more textiles or, in the case of bladders or airbags, oneor more spacer materials, wherein the spacer materials can be textiles,foamed components, 3D printed components, or other materials asdescribed herein.

Additional processes can be performed on the multi-layered films and/orarticles formed therefrom, including, but not limited to, application ofdecorative elements and thermoforming to impart useful structures,shapes, or textures. Also disclosed are consumer products incorporatingthe multi-layered films and articles comprising the same and methods ofmaking the consumer products.

In one exemplary embodiment, provided herein is a method for producingthe multi-layered films disclosed herein, the method comprisingco-extruding the gas-barrier material and the elastomeric material toform a multi-layered structure comprising the one or more core regions.

In one aspect, the method further comprises applying at least one tielayer to the multi-layered film to form a multi-layered film comprisingone or more core regions and the tie layer, wherein the tie layercomprises a tie material as described herein. In some aspects, themethod comprises co-extruding at least one tie layer with themulti-layered film to form a multi-layered film comprising the one ormore core regions and the tie layer.

In another aspect, the method comprises applying at least one structurallayer to the multi-layered film comprising the core region and the tielayer to form a multi-layered film comprising the one or more coreregions, the tie layer, and the structural layer, wherein the structurallayer comprises a structural layer material. Further in this aspect, themethod can comprise co-extruding at least one structural layer with themulti-layered film comprising the core region and the tie layer to forma multi-layered film comprising the one or more core regions, the tielayer, and the structural layer.

In yet another aspect, the method further comprises applying at leastone cap layer to the multi-layered film comprising the core region, thetie layer, and the structural layer to form a multi-layered filmcomprising the core region, the tie layer, the structural layer, and thecap layer, wherein the cap layer comprises a cap layer material asdescribed herein. In some aspects, the method further comprisesco-extruding at least one cap layer with the multi-layered filmcomprising the core region, the tie layer, and the structural layer toform a multi-layered film comprising the core region, the tie layer, thestructural layer, and the cap layer.

In some aspects, the article is a layered sheet, optionally a coextrudedlayered sheet or a laminated layered sheet.

In another aspect, disclosed herein are articles comprising themulti-layered films disclosed herein. In another aspect, the article cancomprise an article of footwear, a component of an article of footwear,an article of apparel, a component of an article of apparel, an articleof sporting equipment, a component of an article of sporting equipment,a personal protective article, a flexible flotation device, a rigidflotation device, a medical device, a prosthetic device, an orthopedicdevice, an accumulator, an article of furniture, or a component of anarticle of furniture. In some aspects, the article can be a tire or ahose. Also disclosed herein are methods of manufacturing a consumerproduct, the methods comprising affixing the disclosed articles to asecond component. Furthermore, disclosed herein are consumer productsproduced by the disclosed methods.

In an aspect, disclosed herein is a polymeric material comprising: oneor more core regions, wherein each of the one or more core regionscomprises a plurality of layers, the plurality of layers comprisinggas-barrier layers comprising at least one gas-barrier materialalternating with elastomeric layers comprising at least one elastomericmaterial, wherein each of the gas-barrier layers is from about 0.5micrometers to about 2 micrometers thick, or from about 0.5 micrometersto about 1 micrometer thick; optionally less than or equal to 0.75micrometers thick, or less than or equal to 0.5 micrometers thick, or ina range of from about 0.01 micrometers to about 0.75 micrometers thick,optionally in a range of from about 0.01 micrometers to about 0.5micrometers thick; and wherein each of the elastomeric layers is fromabout 2 micrometers to about 8 micrometers thick, or from about 2micrometers to about 4 micrometers thick.

In another aspect, each of the one or more core regions comprises atleast 50 layers, or from about 50 to about 100 layers, from about 50 toabout 90 layers, from about 50 to about 80 layers, from about 50 toabout 70 layers, from about 60 to about 100 layers, from about 60 toabout 90 layers, or from about 60 to about 80 layers.

In another aspect, the gas-barrier material comprises or consistsessentially of one or more gas-barrier polymers, wherein the gas-barriermaterial comprises a gas-barrier polymeric component consisting of allpolymers present in the gas-barrier material. In some aspects, thegas-barrier material comprises a nitrogen barrier material.

In an aspect, the one or more gas-barrier polymers comprise or consistessentially of one or more thermoplastic vinylidene chloride polymers,one or more thermoplastic acrylonitrile polymers or copolymers, one ormore thermoplastic polyamides, one or more thermoplastic epoxy resins,one or more thermoplastic amine polymers or copolymers, or one or morethermoplastic polyolefin homopolymers or copolymers. In some aspects,the one or more thermoplastic polyolefin homopolymers or copolymerscomprise or consist essentially of one or more thermoplasticethylene-vinyl alcohol copolymers. In another aspect, the one or morethermoplastic ethylene-vinyl alcohol copolymers include from about 28mole percent to about 44 mole percent ethylene content, or from about 32mole percent to about 44 mole percent ethylene content.

In another aspect, the elastomeric material comprises or consistsessentially of one or more thermoplastic elastomeric polymers, andcomprises an elastomeric polymeric component consisting of all polymerspresent in the elastomeric material. In one aspect, the one or morethermoplastic elastomeric polymers comprise or consist essentially ofone or more thermoplastic elastomeric polyolefin homopolymers orcopolymers, one or more thermoplastic elastomeric polyamide homopolymersor copolymers, one or more thermoplastic elastomeric polyesterhomopolymers or copolymers, one or more thermoplastic elastomericpolyurethane homopolymers or copolymers, one or more thermoplasticelastomeric styrenic homopolymers or copolymers, or any combinationthereof.

In further aspects, the one or more styrenic homopolymers or copolymerscan include one or more styrenic block copolymers, such as acrylonitrilebutadiene styrene block copolymers, styrene acrylonitrile blockcopolymers, styrene ethylene butylene styrene block copolymers, styreneethylene butadiene styrene block copolymers, styrene ethylene propylenestyrene block copolymers, styrene butadiene styrene block copolymers,and combinations thereof.

In some aspects, the elastomeric material comprises or consistsessentially of one or more thermoplastic elastomeric polyurethanehomopolymers or copolymers, and optionally comprises or consistsessentially of one or more polydiene polyol-based thermoplasticelastomeric homopolymers or copolymers.

In one aspect, the one or more thermoplastic elastomeric polyurethanehomopolymers or copolymers comprise a plurality of first segmentsderived from one or more polyols and a plurality of second segmentsderived from a diisocyanate. In another aspect, the one or morethermoplastic elastomeric polyurethane homopolymers or copolymers is apolymerization product of a diisocyanate with a polyol.

In one aspect, the thermoplastic elastomeric polyurethane homopolymer orcopolymer comprises or consists essentially of one or more polydienepolyol-based thermoplastic elastomeric polyurethane homopolymers orcopolymers and the polyol comprises or consists essentially of apolybutadiene polyol, a polyisoprene polyol, a partially orfully-hydrogenated derivative of a polybutadiene polyol or of apolyisoprene polyol, or any combination thereof. In one aspect, thepolyol comprises or consists essentially of a polyester polyol, apolyether polyol, a polycarbonate polyol, a polycaprolactone polyether,or any combination thereof.

In one aspect, the diisocyanate can comprise or consist essentially ofan aliphatic diisocyanate, an aromatic diisocyanate, or any combinationthereof. In one aspect, the aliphatic diisocyanate comprises or consistsessentially of hexamethylene diisocyanate (HDI), isophorone diisocyanate(IPDI), butylenediisocyanate (BDI), bisisocyanatocyclohexylmethane(HMDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI),bisisocyanatomethylcyclohexane, bisisochanatomethyltricyclodecane,norbornane diisocyanate (NDI), cyclohexane diisocyanate (CHDI),4,4′-dicyclohexhylmethane diisocyanate (H12MDI), diisocyanatododecane,lysine diisocyanate, or any combination thereof. In another aspect, thearomatic diisocyanate comprises or consists essentially of toluenediisocyanate (TDI), TDI adducts with trimethylolpropane (TMP), methylenediphenyl diisocyanate (MDI), xylene diisocyanate (XDI),tetramethylxylylene diisocyanate (TMXDI), hydrogenated xylenediisocyanate (HXDI), naphthalene 1,5-diisocyanate (NDI),1,5-tetrahydronaphthalene diisocyanate, para-phenylene diisocyanate(PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 4,4′-dibenzyldiisocyanate (DBDI), 4-chloro-1,3-phenylene diisocyanate, or anycombination thereof.

Additional Materials

In some aspects, the multi-layered films disclosed herein furthercomprise a blended material, wherein the blended material comprises orconsists essentially of a blend of one or more additional thermoplasticelastomers and a second material, optionally wherein the second materialcomprises or consists essentially of one or more second polymers,optionally wherein the one or more second polymers comprise or consistessentially of one or more second thermoplastics.

In an aspect, the one or more second thermoplastics can comprise one ormore thermoplastic polyolefin homopolymers, one or more thermoplasticpolyamide homopolymers or copolymers, one or more thermoplasticpolyester homopolymers or copolymers, one or more thermoplasticpolyurethane homopolymers or copolymers, one or more thermoplasticstyrenic homopolymers or copolymers, or any combination thereof.

In further aspects, the one or more styrenic homopolymers or copolymerscan include one or more styrenic block copolymers, such as acrylonitrilebutadiene styrene block copolymers, styrene acrylonitrile blockcopolymers, styrene ethylene butylene styrene block copolymers, styreneethylene butadiene styrene block copolymers, styrene ethylene propylenestyrene block copolymers, styrene butadiene styrene block copolymers,and combinations thereof.

In another aspect, the one or more second thermoplastics can comprise orconsist essentially of thermoplastic polypropylene homopolymers orcopolymers, thermoplastic polyethylene homopolymers or copolymers,thermoplastic polybutylene homopolymers or copolymers, or anycombination thereof.

In some aspects, the one or more second thermoplastics comprise orconsist essentially of one or more thermoplastic polyethylenecopolymers. In another aspect, the one or more second thermoplasticscomprise or consist essentially of one or more thermoplasticethylene-vinyl alcohol copolymers. In one aspect, a polymeric componentof the blended material consists of one or more additional thermoplasticelastomeric polyurethane homopolymers or copolymers, and one or moresecond thermoplastic ethylene-vinyl alcohol copolymers. In analternative aspect, the polymeric component of the thermoplasticelastomeric material consists of one or more additional thermoplasticelastomeric polyester-polyurethane copolymers and one or more secondthermoplastic ethylene-vinyl alcohol copolymers. In some aspects, theblended material comprises one or more recycled additional thermoplasticelastomers, or one or more recycled second thermoplastics, or both.

In some aspects, the blended material is a phase-separated blend of theone or more additional thermoplastic elastomers and the one or moresecond thermoplastics. In some aspects, the phase-separated blendincludes one or more phase-separated regions including interfacesbetween the one or more additional thermoplastic elastomers and the oneor more second thermoplastics. In some aspects, the blend comprisesabout 95 percent by weight of the one or more second thermoplastics andabout 5 percent by weight of the one or more second thermoplastics basedon a total weight of the blend.

In an aspect, the disclosed multi-layered films further comprise arecycled material comprising one or more recycled polymers, optionallywherein the one or more recycled polymers comprise one or more recycledthermoplastics, optionally wherein the one or more recycledthermoplastics comprise one or more recycled thermoplastic elastomers;optionally wherein the recycled material comprises a recycled materialpolymeric component consisting of one or more recycled thermoplastics,optionally wherein the recycled material polymeric component comprisesor consists essentially of one or more recycled thermoplasticelastomers.

In another aspect, the recycled material can comprise one or morerecycled thermoplastic elastomers, and optionally the one or morerecycled thermoplastic elastomers comprise one or more regroundthermoplastic elastomers, optionally wherein the one or more recycled orreground thermoplastic elastomers includes a thermoplastic elastomericmaterial as disclosed herein.

In some aspects, the recycled material further comprises one or morerecycled second thermoplastics, and the one or more recycled secondthermoplastics optionally comprise one or more reground secondthermoplastics, optionally wherein the one or more recycled or regroundsecond thermoplastics include a thermoplastic as disclosed herein.

In one aspect, the recycled material comprises one or more recycled orreground thermoplastic polyurethane elastomers or one or more recycledor reground thermoplastic ethylene-vinyl alcohol copolymers or both. Inan aspect, the recycled material comprises a blend of the one or morerecycled or reground thermoplastic elastomers and one or more secondthermoplastics, or comprises a blend of one or more thermoplasticelastomers and one or more recycled thermoplastics or one or morerecycled thermoplastics, optionally wherein the blend is aphase-separated blend, and optionally wherein the phase-separated blendcomprises one or more interfaces between the one or more recycledthermoplastic elastomers and the one or more second thermoplastics.

In another aspect, in the multi-layered films, the recycled materialcomprises about 99 percent to about 90 percent by weight of the one ormore recycled thermoplastic elastomers and about 1 percent to about 10percent by weight of the one or more second thermoplastics based on atotal weight of the recycled material, optionally wherein the recycledmaterial comprises about 99 percent to about 93 percent by weight of theone or more recycled thermoplastic elastomers and about 1 percent toabout 7 percent by weight of the one or more second thermoplastics, orabout 99 percent to about 95 percent by weight of the one or morerecycled thermoplastic elastomers and about 1 percent to about 5 percentby weight of the one or more second thermoplastic elastomers.

In an aspect, the recycled material comprises about 99 percent to about50 percent by weight of recycled or reground polymers based on a totalweight of recycled material, or from about 99 percent to about 75percent by weight of recycled or reground polymers.

In some aspects, the recycled material further comprises one or morevirgin first thermoplastic elastomers, optionally wherein the one ormore virgin thermoplastic elastomers includes one or more virginthermoplastic polyurethane elastomers.

In one aspect, the multi-layered film further comprises one or more tielayers, each of the one or more tie layers individually comprising orconsisting essentially of a tie material, wherein the one or more tielayers increase a bond strength between two adjacent layers. In someaspects, the tie material of each of the one or more tie layersindependently comprises or consists essentially of a polyurethane, apolyacrylate, an ethylene-acrylate copolymer, a maleic anhydride graftedpolyolefin, or any combination thereof, and optionally the tie materialcomprises or consists essentially of a blended material or a recycledmaterial as disclosed herein. In another aspect, the tie layer materialof the one or more tie layers independently comprises or consistsessentially of one or more thermoplastic polyurethane elastomerichomopolymers or copolymers, optionally wherein the one or more tielayers comprise or consist essentially of polydiene polyol-basedthermoplastic polyurethane.

In another aspect, the multi-layered films further comprise one or morestructural layers, each of the one or more structural layersindependently comprising or consisting essentially of a structural layermaterial, optionally wherein the structural layer material comprises orconsists essentially of a blended material or a recycled material asdescribed herein. In some aspects, the structural layer material of theone or more structural layers independently comprises or consistsessentially of a polydiene polyol-based thermoplastic polyurethane.

In still another aspect, the multi-layered films can comprise one ormore cap layers, wherein the one or more cap layers comprise or consistessentially of a cap layer material, optionally wherein the cap layermaterial comprises or consists essentially of a blended material or arecycled material as disclosed herein. In some aspects, the cap layermaterial of the one or more cap layers comprises or consists essentiallyof a polyurethane, a polyacrylate, an ethylene-acrylate copolymer, amaleic anhydride grafted polyolefin, or any combination thereof. Inanother aspect, the cap layer material of the one or more cap layerscomprises or consists essentially of a thermoplastic polyurethane,optionally a polydiene polyol-based thermoplastic polyurethane.

In some aspects, at least one of the one or more tie layers ispositioned between one of the one or more structural layers and one ofthe one or more core regions. In another aspect, at least one of the oneor more structural layers is positioned between one of the one or moretie layers and one of the one or more cap layers. In another aspect, themulti-layered film can be a coextruded layered sheet or a laminatedlayered sheet.

In one aspect, disclosed herein is a multi-layered film comprising afirst cap layer, a first structural layer, a first tie layer, a coreregion, a second tie layer, a second structural layer, and a second caplayer, wherein a first cap layer inner surface contacts a first surfaceof the first structural layer, a second surface of the first structurallayer contacts a first surface of the first tie layer, a second surfaceof the first tie layer contacts a first surface of the core region, asecond surface of the core region contacts a first surface of the secondtie layer, a second surface of the second tie layer contacts a firstsurface of the second structural layer, and a second surface of thesecond structural layer contacts an inner layer of the second cap layer.

In an alternative aspect, the disclosed multi-layered films have astructure of A-B-C-B-A, wherein A represents a structural layer, Brepresents a tie layer, and C represents a core region. In anotheraspect, the disclosed multi-layered films have a structure ofD-A-B-C-B-A-D, wherein A represents a structural layer, B represents atie layer, C represents a core region, and D represents a cap layer.

In an aspect, in any of the disclosed multi-layered films, each of theone or more core regions can have a gas transmission rate of from about0.3 to about 1.9 cubic centimeters per square meter per day for nitrogenmeasured at 23 degrees Celsius and 0 percent relative humidity for astructure having a thickness of from about 72 micrometers to about 320micrometers.

In any of these aspects, the multi-layered film further comprises one ormore protective layers, each of the one or more protective layersindividually comprising or consisting essentially of a protectivematerial, wherein each of the one or more protective layers is adjacentto a core region and has a protective layer thickness, wherein acombination of the one or more protective layers and the adjacent coreregion has a minimum radius of curvature which is greater than a minimumradius of curvature which causes cracking of the core region, or of oneor more individual layers within the core region.

Methods for Producing the Multi-Layered Films

In an aspect, the sheets comprising gas-barrier layers can be producedby co-extrusion followed by vacuum thermoforming to form the profile ofthe airsole which can optionally include one or more valves (e.g., oneway valves) that allows the airsole to be filled with the fluid (e.g.,gas).

In any of these aspects, the multi-layered films and articles producedtherefrom are suitable for use in mass-market products including, butnot limited to, articles of footwear, articles of sporting equipment,articles of athletic apparel, personal protective equipment, and thelike.

In an aspect, the multi-layered films and articles formed therefrom caninclude one or more textiles or, in the case of bladders or airbags, oneor more spacer materials, wherein the spacer materials can be textiles,foamed components, 3D printed components, or other materials asdescribed herein.

Additional processes can be performed on the multi-layered films and/orarticles formed therefrom, including, but not limited to, application ofdecorative elements and thermoforming to impart useful structures,shapes, or textures. Also disclosed are consumer products incorporatingthe multi-layered films and articles comprising the same and methods ofmaking the consumer products.

In one embodiment, provided herein is a method for manufacturing themulti-layered films disclosed herein, the method including at least thesteps of co-extruding the gas barrier material and the elastomericmaterial to form a multi-layered film comprising one or more coreregions, wherein each of the one or more core regions comprises aplurality of layers, the plurality of layers comprising gas-barrierlayers comprising the gas-barrier material alternating with elastomericlayers comprising the elastomeric material.

In one aspect, the disclosed method further comprises applying at leastone tie layer to the multi-layered film comprising the one or more coreregions to form a multi-layered film comprising the one or more coreregions and the tie layer, wherein the tie layer comprises a tiematerial as disclosed herein. In a further aspect, the disclosed methodfurther comprises co-extruding at least one tie layer with themulti-layered film comprising the core region to form a multi-layeredfilm comprising the one or more core regions and the tie layer.

In one aspect, the disclosed method further comprises applying at leastone structural layer to the multi-layered film comprising the coreregion and the tie layer to form a multi-layered film comprising the oneor more core regions, the tie layer, and the structural layer, whereinthe structural layer comprises a structural layer material as disclosedherein. In an alternative aspect, the disclosed method further comprisesco-extruding at least one structural layer with the multi-layered filmcomprising the core region and the tie layer to form a multi-layeredfilm comprising the one or more core regions, the tie layer, and thestructural layer.

In one aspect, the disclosed method further comprises applying at leastone cap layer to the multi-layered film comprising the core region, thetie layer, and the structural layer to form a multi-layered filmcomprising the core region, the tie layer, the structural layer, and thecap layer, wherein the cap layer comprises a cap layer material asdisclosed herein. In an alternative aspect, the disclosed method furthercomprises co-extruding at least one cap layer with the multi-layeredfilm comprising the core region, the tie layer, and the structural layerto form a multi-layered film comprising the core region, the tie layer,the structural layer, and the cap layer.

In an exemplary embodiment, disclosed herein are multi-layered filmsproduced by the disclosed methods.

Articles

In one aspect, provided herein are articles comprising the multi-layeredfilms disclosed herein, the articles including: a multi-layered filmcomprising

-   -   a first cap layer comprising or consisting essentially of a        first cap layer material, the first cap layer including a first        cap layer outer surface defining a first outer surface of the        multi-layered film, a first cap inner layer surface opposing the        first cap layer outer surface, a first cap layer thickness        extending from the first cap layer inner surface to the first        cap layer outer surface, wherein the first cap layer outer        surface defines a first exterior surface of the article;    -   a second cap layer comprising or consisting essentially of a        second cap layer material, the second cap layer including a        second cap layer outer surface defining a second outer surface        of the multi-layered film, a second cap layer inner surface        opposing the second cap layer outer surface, a second cap layer        thickness extending from the second cap layer inner surface to        the second cap layer outer surface, optionally wherein the        second cap layer outer surface defines a second exterior surface        of the article; and    -   one or more core regions, wherein each of the one or more core        regions comprises or consists essentially of one or more        gas-barrier layers, optionally one or more gas-barrier layers        each having an average thickness of less than or equal to about        0.75 micrometers, optionally at least about 20 individual        gas-barrier layers, each gas-barrier layer alternating with        elastomeric layers, each of the one or more core regions        including a core region first surface, a core region second        surface, and a core region thickness extending from the core        region first surface to the core region second surface, wherein        each of the one or more core regions is positioned between the        first cap layer inner surface and the second cap layer inner        surface.

In another aspect, the first cap layer material and the second cap layermaterial are substantially the same. In an alternative aspect, the firstcap layer material and the second cap layer material are different. Insome aspects, the first cap layer inner surface is in contact with thecore region first surface, or the second cap layer inner surface is incontact with the core region second surface, or both.

In another aspect, the article can be configured as a series of four ormore layers including one or more structural layers, each of the one ormore structural layers comprising a structural layer material andincluding a structural layer first surface, a structural layer secondsurface opposing the structural layer first surface, and a structurallayer thickness extending from the structural layer first surface to thestructural layer second surface;

-   -   optionally wherein at least one of the one or more structural        layers is positioned between the first cap layer and the core        region, or between the second cap layer and the core region; or    -   optionally wherein the one or more structural layers comprise        two or more structural layers, and at least a first one of the        two or more structural layers is positioned between an inner        surface of a first cap layer and the first surface of a core        region, and at least a second one of the two or more structural        layers is positioned between a second surface of a core region        and the inner surface of the second cap layer.

In another aspect, a first surface of a first one of the structurallayers is in contact with the inner surface of the first cap layer, andthe second surface of the first one of the structural layers is incontact with a first surface of one of the one or more core regions, orthe first surface of a second one of the one or more structural layersis in contact with the second surface of one of the one or more coreregions, and the second surface of the second one of the structurallayers is in contact with an inner surface of the second cap layer, orboth.

In one aspect, the one or more structural layers comprise or consistessentially of the blended material or the recycled material asdisclosed herein.

In an aspect, the article can be configured as a series of five or morelayers including one or more tie layers, each of the one or more tielayers including a tie layer first surface, a tie layer second surfaceopposing the tie layer first surface, and a tie layer thicknessextending from the tie layer first surface to the tie layer secondsurface;

-   -   optionally wherein at least one of the one or more tie layers is        positioned between one of the one or more structural layers and        one of the one or more core regions, or between the first cap        layer and one of the one or more structural layers, or between        the second cap layer and one of the one or more structural        layers, or any combination thereof; or    -   optionally wherein the one or more tie layers comprise two or        more tie layers, and at least a first one of the two or more tie        layers is positioned between a second surface of a first        structural layer and a first layer of a core region, and at        least a second one of the two or more tie layers is positioned        between a second surface of a core region and a first surface of        a structural layer.

In one aspect, a first surface of a first one of the one or more tielayers is in contact with a second surface of a first one of the one ormore structural layers, and the second surface of the first one of theone or more tie layers is in contact with a first surface of a coreregion, or wherein a first surface of a second one of the one or moretie layers is in contact with a second surface of one of the one or morecore regions, and the second surface of the second one of the one ormore tie layers is in contact with a first surface of a second one ofthe one or more structural layers, or both.

In an aspect, the article comprises the first cap layer, a firststructural layer, a first tie layer, a core region, a second tie layer,a second structural layer, and the second cap layer, wherein the firstcap layer inner surface contacts the first surface of the firststructural layer, the second surface of the first structural layercontacts the first surface of the first tie layer, the second surface ofthe first tie layer contacts the first surface of the core region, thesecond surface of the core region contacts the first surface of thesecond tie layer, the second surface of the second tie layer contactsthe first surface of the second structural layer, and the second surfaceof the second structural layer contacts the inner layer of the secondcap layer, and optionally the core region comprises one or more coreregions, or comprises a plurality of microlayers.

In some aspects, the article is a layered sheet, optionally a coextrudedlayered sheet or a laminated layered sheet.

In another aspect, disclosed herein are articles comprising themulti-layered films disclosed herein. In another aspect, the article cancomprise an article of footwear, a component of an article of footwear,an article of apparel, a component of an article of apparel, an articleof sporting equipment, a component of an article of sporting equipment,a personal protective article, a flexible flotation device, a rigidflotation device, a medical device, a prosthetic device, an orthopedicdevice, an accumulator, an article of furniture, or a component of anarticle of furniture. In some aspects, the article can be a tire or ahose. Also disclosed herein are methods of manufacturing a consumerproduct, the methods comprising affixing the disclosed articles to asecond component. In a further aspect, disclosed herein are consumerproducts produced by the disclosed methods.

Thermoforming

In any of the foregoing aspects, the multi-layered films or bladder canbe subjected to a thermoforming step, optionally wherein thermoformingoccurs before inflation of the bladder, or wherein the thermoformingstep occurs simultaneously with the inflation of the bladder, or whereinthe thermoforming step occurs after the inflation of the bladder. In oneaspect, thermoforming the bladder can impart one or more structural orother properties to the bladder, such as three-dimensional shape orstructure, rigidity, abrasion resistance, water resistance, or the like,to one or more portions of the bladder. In some aspects, thethermoforming process can be useful in imparting a texture to thebladder, wherein the texture can be decorative, functional, or bothdecorative and functional.

In an aspect, a portion of the multi-layered films or bladder can beselectively thermoformed, for example, by masking portions of themulti-layered films or bladder that are not desired to be exposed to thethermoforming process, or by using tooling that contacts or covers onlya portion of the multi-layered films or bladder.

In one aspect, the multi-layered films or bladder comprise an outersurface and thermoforming comprises placing the multi-layered films orbladder in a mold, wherein the mold comprises an inner molding surface.Further in this aspect, the inner molding surface contacts the outersurface of the multi-layered films or bladder.

In some aspects, a protective sheath having an outer surface is placedbetween at least a portion of the outer surface of the multi-layeredfilm or bladder and the inner molding surface, and the outer surface ofthe protective sheath contacts the inner molding surface. In a furtheraspect, the protective sheath comprises an inner surface and the innersurface of the protective sheath contacts the outer surface of themulti-layered film or bladder. In an optional aspect, the inner surfaceof the protective sheath comprises a raised pattern. In some aspects,the raised pattern of the inner surface of the protective sheath isimprinted into the multi-layered film or bladder during thermoforming.In one aspect, use of a protective sheath may be effective in reducingthe number of air bubbles that form and become trapped in any layer ofthe multi-layered film or bladder during the thermoforming process.

In an aspect, thermoforming further comprises applying a compressiveforce between the outer surface of the multi-layered film or bladder andthe inner molding surface, or optionally between the outer surface ofthe protective sheath and the inner molding surface. In some aspects,the compressive force provides a pressure differential between the outersurface of the multi-layered film or bladder and the inner moldingsurface, or optionally between the outer surface of the protectivesheath and the inner molding surface. In one aspect, the pressuredifferential can be a positive pressure differential. In another aspect,the pressure differential can be a negative pressure differential.

In any of these aspects, following thermoforming, the bladder can becooled. During and after cooling, in an aspect, the bladder retainsshape and/or other properties imparted during or as a result of thedisclosed thermoforming process.

In some aspects, thermoforming comprises increasing a temperature of themulti-layered films or bladder to a softening temperature of the firstsheet, the second sheet, or both, conforming the outer surface of themulti-layered films or bladder to the shape of the inner moldingsurface.

Decoration

In one aspect, disclosed herein is a multi-layered film or a bladder,wherein the multi-layered film or bladder further comprises a decorativeelement.

Also disclosed herein is a method for applying a decorative element to amulti-layered film or bladder. In one aspect, the method comprisesapplying the decorative element by printing, painting, brushing, orspraying the decorative element onto the multi-layered film or bladder.In another aspect, the method comprises dipping the multi-layered filmor bladder into the decorative element, or pressing the decorativeelement into the multi-layered film or bladder. In an aspect, thedecorative element is in the form of a solid, a liquid, or a gas whenapplied to the multi-layered film or bladder. In an optional aspect, thedecorative element comprises a pigment or a dye or both a pigment and adye.

In one aspect, the decorative element comprises pigments or dyes or bothand the step of applying the decorative element onto the multi-layeredfilm or bladder comprises curing the decorative element on themulti-layered film or bladder, optionally wherein the curing comprisesdrying the decorative element, crosslinking the decorative element, orinfusing at least a portion of the decorative element into a polymericmaterial of an exterior surface of the multi-layered film or bladder, orbonding the decorative element to the exterior surface of themulti-layered film or bladder, or any combination thereof.

In another aspect, the method includes the step of bonding thedecorative element to the exterior surface of the multi-layered film orbladder, and the bonding includes forming an adhesive bond by applyingan adhesive to a first side of the decorative element or to the exteriorsurface of the multi-layered film or bladder, or both, and then pressingtogether the first side of the decorative element and the exteriorsurface of the multi-layered film or bladder.

In an alternative aspect, the method includes the step of bonding thedecorative element to the exterior surface of the multi-layered film orbladder, and the bonding includes forming a thermal bond between athermoplastic material of a first side of the decorative element and athermoplastic material defining the exterior surface of themulti-layered film or bladder, by softening or melting at least an outerportion of one or both of the thermoplastic materials, and pressing thefirst side of the decorative element and the exterior surface of themulti-layered film or bladder against each other while one or both ofthe thermoplastic materials are softened or melted, and thenre-solidifying the softened or melted outer portion.

In an aspect, the decorative element is applied to an exterior surfaceof the multi-layered film or bladder, and, during applying or duringcuring or during both the applying and the curing, the decorativeelement infuses into a material defining the exterior surface of themulti-layered film or bladder, optionally wherein the decorative elementis applied as a solution of a dye.

Also disclosed herein are multi-layered films and/or bladders comprisinga decorative element applied according to any one of the disclosedmethods.

Articles Incorporating the Multi-Layered Films

Sole Structures. In an aspect, disclosed herein is a sole structure foran article of footwear having an upper, the sole structure comprising aheel region disposed in a posterior end; a forefoot region disposed inan anterior end; a mid-foot region disposed intermediately between theheel region and the forefoot region; and a bladder as disclosed herein.In one aspect, the bladder is disposed in the heel region.

Also disclosed are articles of footwear comprising the disclosedbladders, and articles of footwear comprising the disclosed solestructures.

In one aspect, disclosed herein is an article of footwear comprising anupper and a sole structure, wherein the upper, the sole structure, orboth the upper and the sole structure comprise a bladder, the bladdercomprising:

-   -   a first film secured to a second film to define a sealed        internal cavity; and    -   a fluid disposed within the sealed internal cavity at a pressure        of about one atmosphere (101 kilopascals) or greater;    -   wherein the first film, the second film or each of the first        film and the second film is a multi-layered film including a        core region comprising at least 50 gas-barrier layers and a        plurality of elastomeric layers, wherein the gas-barrier layers        alternate with the elastomeric layers, wherein each of the        gas-barrier layers comprises at least one gas-barrier material,        and wherein each of the elastomeric layers comprises at least        one elastomeric material, and wherein the core region has a        total thickness less than 200 micrometers.

In one aspect, the sole structure comprises the bladder. In anotheraspect, the article of footwear further comprises a chassis secured tothe upper. In still another aspect, the article of footwear furthercomprises an outsole and, optionally, the outsole is secured to thebladder. In some aspects, in the article of footwear, the bladder can bedisposed between the chassis and the outsole.

Sporting Equipment. In another aspect, disclosed herein are articles ofsporting equipment comprising the multi-layered films. Further in thisaspect, the articles of athletic equipment include any articles whereflexibility and gas-barrier properties are useful, such as, for example,inflatable balls, rafts, watercraft, mats, balance trainers, flotationdevices, and the like.

Referring now to FIG. 7A, in one non-limiting aspect, the multi-layeredfilms can be incorporated into a soccer ball. Further in this aspect,the soccer ball can have outer covering 4000, one or more intermediatelayers (shown herein as 4010 a, 4010 b, and 4010 c, although otherembodiments having more or fewer intermediate layers should also beconsidered disclosed), and an innermost gas-barrier layer 4020comprising the disclosed multi-layered film, wherein gas-barrier layer4020 allows the soccer ball to maintain an inflated state during play byreducing rates of gas (e.g., inflation air) transmission through themulti-layered film. FIG. 7B shows a cross-section of the soccer ball ofFIG. 7A, wherein the positioning between an innermost intermediate layer4010 c and the multi-layered film 4020 comprising alternatinggas-barrier layers 4040 and elastomeric layers 4050. Interior 4030 ishollow and, upon inflation of the ball, is filled with air or anothergas. Interior 4030 is surrounded by the multi-layered film 4020, whichprovides for a low gas-transmission rate (e.g. less than about 0.5 toabout 2 cubic centimeters per square meter per day for nitrogen measuredat 23 degrees Celsius and 0 percent relative humidity for a film havinga thickness ranging from 72 micrometers to 320 micrometers).

Transportation Equipment. In still another aspect, disclosed herein arearticles useful in transportation comprising the multi-layered films. Inone aspect, the article can be a tire for a bicycle, automobile,tractor, motorized scooter, motorcycle, or any other vehicle usinginflatable tires.

An exemplary tire is shown in FIGS. 8A and 8B. In one aspect, outersurface 5000 of the tire can display a pattern of treads for improvedtraction and/or other aspects of operation on a road or track. Furtherin this aspect, the tire can comprise rubber or another material 5010that is, in some aspects, vulcanized to enhance strength, flexibility,and durability of the tire. In any of these aspects, inner layer of thetire 5020 comprises the multi-layered film disclosed herein, which, insome aspects, provides a surface area reducing gas transmission in orderto maintain inflation of the tire during use.

In one aspect, the multi-layered film can cover the entire inner surfaceof the tire including the sidewalls (shown). In an alternative aspect,the multi-layered film can cover a portion of the tire. The disclosedtires can incorporate tubes or can be tubeless tires and can furtherinclude any other layers commonly associated with a particular use (e.g.belts, noise reduction devices, and the like, for automobile tires) inaddition to the disclosed multi-layered films.

Property Analysis and Characterization Procedures

Specific Gravity/Density Test Protocol. The specific gravity (S.G.) ordensity is measured for samples taken using the Component SamplingProcedure as described herein, using a digital balance or a DensicomTester (Qualitest, Plantation, Fla., USA). Each sample is weighed andthen is submerged in a distilled water bath (at 22 degrees Celsius plusor minus 2 degrees Celsius). To avoid errors, air bubbles on the surfaceof the samples are removed, e.g., by wiping isopropyl alcohol on thesample before immersing the sample in water, or using a brush after thesample is immersed. The weight of the sample in the distilled water isrecorded. The specific gravity is calculated using the followingformula:

${S.{G.}} = \frac{{Weight}{of}{the}{sample}{in}{air}(g)}{{{Weight}{of}{sample}{in}{air}(g)} - {{Weight}{of}{sample}{in}{water}(g)}}$

Melting Temperature, Glass Transition Temperature, and Enthalpy ofMelting Test Protocol. The melting temperature and glass transitiontemperature are determined using a commercially available DifferentialScanning Calorimeter (“DSC”) in accordance with ASTM D3418-97, using asample prepared using the Material Sampling Procedure. Briefly, a 10-15gram sample is placed into an aluminum DSC pan and then the lid issealed with a crimper press. The DSC is configured to scan from −100degrees Celsius to 225 degrees Celsius with a 20 degree Celsius perminute heating rate, hold at 225 degrees Celsius for 2 minutes, and thencool down to 25 degrees Celsius at a rate of −10 degrees Celsius perminute. The DSC curve created from this scan is then analyzed usingstandard techniques to determine the glass transition temperature andthe melting temperature. The enthalpy of melting is calculated byintegrating the area of the melting endotherm peak and normalizing bythe sample mass.

Alternatively, glass transition temperature can be determined usingDynamic Mechanical Analysis (DMA). In this technique, a piece of themulti-layered film about 1 millimeter thick, about 5 millimeters toabout 10 millimeters wide and about 20 millimeters long is mounted on afilm tension fixture of a DMA apparatus. The sample is heated over apre-determined temperature range at a fixed rate of, for example, about1 degree Celsius to about 5 degrees Celsius per minute. During heating,the sample is tested at fixed frequency (e.g., about 1 Hertz) and asmall oscillation amplitude (e.g. about 0.05 percent strain). Thestorage modulus (or complex shear) is recorded.

G′ is the storage modulus, representing elastic portion of theviscoelastic material. G″ is the loss modulus, representing the viscousportion. G′ measures the energy stored and G″ measures the energylost/dissipated as heat. Tan delta is the ratio of G″/G′ and the peakregion is indicative of the glass transition temperature of the sample.

Melt Flow Index Test Protocol. The melt flow index is determinedaccording to the test method detailed in ASTM D1238-13 Standard TestMethod for Melt Flow Rates of Thermoplastics by Extrusion Plastometer,using Procedure A described therein. Briefly, the melt flow indexmeasures the rate of extrusion of thermoplastics through an orifice at aprescribed temperature and load. In the test method, approximately 7grams of the material is loaded into the barrel of the melt flowapparatus, which has been heated to a temperature specified for thematerial. A weight specified for the material is applied to a plungerand the molten material is forced through the die. A timed extrudate iscollected and weighed. Melt flow rate values are calculated in grams/10minutes.

Creep Relaxation Temperature Test Protocol. The creep relationtemperature is determined according to the exemplary techniquesdescribed in U.S. Pat. No. 5,866,058. The creep relaxation temperatureis calculated to be the temperature at which the stress relaxationmodulus of the tested material is 10 percent relative to the stressrelaxation modulus of the tested material at the solidificationtemperature of the material, where the stress relaxation modulus ismeasured according to ASTM E328-02. The solidification temperature isdefined as the temperature at which there is little to no change in thestress relaxation modulus or little to no creep about 300 seconds aftera stress is applied to a test material, which can be observed byplotting the stress relaxation modulus (in Pascals) as a function oftemperature (in degrees Celsius).

KIM Test Protocol. For each KIM test, a multi-layered article asdescribed herein is extruded and formed into a cushioning devicecomponent having an average wall thickness of between 400 micrometersand 1000 micrometers. Upon inflating the cushioning device to 15.0pound-force per square inch to 25.0 pound-force per square inch (about103 kilopascals to about 172 kilopascals) with nitrogen gas, thecushioning device is intermittently compressed by a reciprocating pistonhaving a 4.0, 5.0, or 6.0 inch diameter platen, or by a platen having ageometry similar to a shoe last to distribute forces evenly across anentire airsole. The stroke of each piston is calibrated as follows. Themulti-layered article is first subjected to a force-controlled testwherein the multi-layered article is taken to a peak load of 2250Newtons, resulting in from about 25 percent to about 70 percentcompression based on inflation pressure. The displacement at this peakload is recorded and used to set the peak displacement in the KIM test,using a gage block. A typical KIM test is run to a predetermined cyclecount such as 320,000 or 400,000 cycles to mimic a mileage count for anaverage athlete (e.g. 175 pounds and 6 feet tall).

Sampling Procedures

Using the Test Protocols described above, various properties of thematerials disclosed herein and articles formed therefrom can becharacterized using samples prepared with the following samplingprocedures.

Material Sampling Procedure. The Material Sampling Procedure can be usedto obtain a neat sample of a polymeric material or of a polymer, or, insome instances, a sample of a material used to form a polymeric materialor a polymer. The material is provided in media form, such as flakes,granules, powders, pellets, or the like. If a source of the polymericmaterial or polymer is not available in a neat form, the sample can becut from a component or element containing the polymeric material orpolymer, such as a composite element or a sole structure, therebyisolating a sample of the material.

Component Sampling Procedure. This procedure can be used to obtain asample of a material from a component of an article of footwear, anarticle of footwear, a component of an article of apparel, an article ofapparel, a component of an article of sporting equipment, or an articleof sporting equipment. A sample including the material in a non-wetstate (e.g., at 25 degrees Celsius and 20 percent relative humidity) iscut from the article or component using a blade. If the material isbonded to one or more additional materials, the procedure can includeseparating the additional materials from the material to be tested.

The sample is taken at a location along the article or component thatprovides a substantially constant material thickness for the material aspresent on the article or component (within plus or minus 10 percent ofthe average material thickness). For many of the test protocolsdescribed above, a sample having a surface area of 4 square centimetersis used. The sample is cut into a size and shape (e.g., a dogbone-shapedsample) to fit into the testing apparatus. In cases where the materialis not present on the article or component in any segment having a 4square centimeter surface area and/or where the material thickness isnot substantially constant for a segment having a 4 square centimetersurface area, sample sizes with smaller cross-sectional surface areascan be taken and the area-specific measurements are adjustedaccordingly.

Definitions

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this disclosure belongs. It will be further understoodthat terms, such as those defined in commonly used dictionaries, shouldbe interpreted as having a meaning that is consistent with their meaningin the context of the specification and relevant art and should not beinterpreted in an idealized or overly formal sense unless expresslydefined herein.

All publications, patents, and patent applications cited in thisspecification are cited to disclose and describe the methods and/ormaterials in connection with which the publications are cited. All suchpublications, patents, and patent applications are herein incorporatedby references as if each individual publication or patent werespecifically and individually indicated to be incorporated by reference.Such incorporation by reference is expressly limited to the methodsand/or materials described in the cited publications, patents, andpatent applications and does not extend to any lexicographicaldefinitions from the cited publications, patents, and patentapplications. Any lexicographical definition in the publications,patents, and patent applications cited that is not also expresslyrepeated in the instant specification should not be treated as such andshould not be read as defining any terms appearing in the accompanyingclaims.

This disclosure is not limited to particular aspects, embodiments, orexamples described, and as such can, of course, vary. The terminologyused herein serves the purpose of describing particular aspects,embodiments, and examples only, and is not intended to be limiting,since the scope of the present disclosure will be limited only by theappended claims.

Where a range of values is provided, each intervening value, to thetenth of the unit of the lower limit unless the context clearly dictatesotherwise, between the upper and lower limit of that range and any otherstated or intervening value in that stated range, is encompassed withinthe disclosure. The upper and lower limits of these smaller ranges canindependently be included in the smaller ranges and are also encompassedwithin the disclosure, subject to any specifically excluded limit in thestated range. Where the stated range includes one or both of the limits,ranges excluding either or both of those included limits are alsoincluded in the disclosure.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual aspects, embodiments and examplesdescribed and illustrated herein has discrete components and featureswhich can be readily separated from or combined with the features of anyof the other several aspects, embodiments, and examples withoutdeparting from the scope or spirit of the present disclosure. Anyrecited method can be carried out in the order of events recited or inany other order that is logically possible.

Although any methods and materials similar or equivalent to thosedescribed herein can also be used in the practice or testing of thepresent disclosure, the preferred methods and materials are nowdescribed. Functions or constructions well-known in the art cannot bedescribed in detail for brevity and/or clarity. Aspects of the presentdisclosure will employ, unless otherwise indicated, techniques ofnanotechnology, organic chemistry, materials science and engineering andthe like, which are within the skill of the art. Such techniques areexplained fully in the literature.

It should be noted that ratios, concentrations, amounts, and othernumerical data can be expressed herein in a range format. Where thestated range includes one or both of the limits, ranges excluding eitheror both of those included limits are also included in the disclosure,e.g. the phrase “x to y” includes the range from ‘x’ to ‘y’ as well asthe range greater than ‘x’ and less than ‘y.’ The range can also beexpressed as an upper limit, e.g. ‘about x, y, z, or less’ and should beinterpreted to include the specific ranges of ‘about x,’ ‘about y,’ and‘about z’ as well as the ranges of ‘less than x,’ less than y,’ and‘less than z.’ Likewise, the phrase ‘about x, y, z, or greater’ shouldbe interpreted to include the specific ranges of ‘about x,” about y,’and ‘about z’ as well as the ranges of ‘greater than x,’ greater thany,′ and ‘greater than z.’ In addition, the phrase “about ‘x’ to ‘y’”,where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about‘y’”. It is to be understood that such a range format is used forconvenience and brevity, and thus, should be interpreted in a flexiblemanner to include not only the numerical values explicitly recited asthe limits of the range, but also to include all the individualnumerical values or sub-ranges encompassed within that range as if eachnumerical value and sub-range is explicitly recited. To illustrate, anumerical range of “about 0.1 percent to 5 percent” should beinterpreted to include not only the explicitly recited values of about0.1 percent to about 5 percent, but also include individual values(e.g., 1 percent, 2 percent, 3 percent, and 4 percent) and thesub-ranges (e.g., 0.5 percent, 1.1 percent, 2.4 percent, 3.2 percent,and 4.4 percent) within the indicated range.

As used herein, the term “polymer” refers to a chemical compound formedof a plurality of repeating structural units referred to as monomers.Polymers often are formed by a polymerization reaction in which theplurality of structural units become covalently bonded together. Whenthe monomer units forming the polymer all have the same chemicalstructure, the polymer is a homopolymer. When the polymer includes twoor more monomer units having different chemical structures, the polymeris a copolymer. One example of a type of copolymer is a terpolymer,which includes three different types of monomer units. The co-polymercan include two or more different monomers randomly distributed in thepolymer (e.g., a random co-polymer). Alternatively, one or more blockscontaining a plurality of a first type of monomer can be bonded to oneor more blocks containing a plurality of a second type of monomer,forming a block copolymer. A single monomer unit can include one or moredifferent chemical functional groups.

Polymers having repeating units which include two or more types ofchemical functional groups can be referred to as having two or moresegments. For example, a polymer having repeating units of the samechemical structure can be referred to as having repeating segments.Segments are commonly described as being relatively harder or softerbased on their chemical structures, and it is common for polymers toinclude relatively harder segments and relatively softer segments bondedto each other in a single monomeric unit or in different monomericunits. When the polymer includes repeating segments, physicalinteractions or chemical bonds can be present within the segments orbetween the segments or both within and between the segments. Examplesof segments often referred to as “hard segments” include segmentsincluding a urethane linkage, which can be formed from reacting anisocyanate with a polyol to form a polyurethane. Examples of segmentsoften referred to as “soft segments” include segments including analkoxy functional group, such as segments including ether or esterfunctional groups, and polyester segments. Segments can be referred tobased on the name of the functional group present in the segment (e.g.,a polyether segment, a polyester segment), as well as based on the nameof the chemical structure which was reacted in order to form the segment(e.g., a polyol-derived segment, an isocyanate-derived segment). Whenreferring to segments of a particular functional group or of aparticular chemical structure from which the segment was derived, it isunderstood that the polymer can contain up to 10 mole percent ofsegments of other functional groups or derived from other chemicalstructures. For example, as used herein, a polyether segment isunderstood to include up to 10 mole percent of non-polyether segments.

The terms “Material Sampling Procedure” and “Component SamplingProcedure” as used herein refer to the respective sampling proceduresand test methodologies described in the Property Analysis andCharacterization Procedure section. These sampling procedures and testmethodologies characterize the properties of the recited materials,films, articles and components, and the like, and are not required to beperformed as active steps in the claims.

The term “about,” as used herein, can include traditional roundingaccording to significant figures of the numerical value. In someaspects, the term about is used herein to mean a deviation of 10percent, 5 percent, 2.5 percent, 1 percent, 0.5 percent, 0.1 percent,0.01 percent, or less from the specified value.

The articles “a” and “an,” as used herein, mean one or more when appliedto any feature in aspects of the present disclosure described in thespecification and claims. The use of “a” and “an” does not limit themeaning to a single feature unless such a limit is specifically stated.The article “the” preceding singular or plural nouns or noun phrasesdenotes a particular specified feature or particular specified featuresand can have a singular or plural connotation depending upon the contextin which it is used.

As used herein, the terms “about,” “approximate,” “at or about,” and“substantially” mean that the amount or value in question can be theexact value or a value that provides equivalent results or effects asrecited in the claims or taught herein. That is, it is understood thatamounts, sizes, formulations, parameters, and other quantities andcharacteristics are not and need not be exact, but can be approximateand/or larger or smaller, as desired, reflecting tolerances, conversionfactors, rounding off, measurement error and the like, and other factorsknown to those of skill in the art such that equivalent results oreffects are obtained. In some circumstances, the value that providesequivalent results or effects cannot be reasonably determined. In suchcases, it is generally understood, as used herein, that “about” and “ator about” mean the nominal value indicated ±10 percent variation unlessotherwise indicated or inferred. In general, an amount, size,formulation, parameter or other quantity or characteristic is “about,”“approximate,” or “at or about” whether or not expressly stated to besuch. It is understood that where “about,” “approximate,” or “at orabout” is used before a quantitative value, the parameter also includesthe specific quantitative value itself, unless specifically statedotherwise.

As used herein, the phrase “consists essentially of” or “consistingessentially of” refer to the feature being disclosed as having primarilythe listed feature without other active components (relative to thelisted feature) and/or those that do not materially affect thecharacteristic(s) of the listed feature. For example, the gas-barriermaterial can consist essentially of a gas-barrier material, which meansthat gas-barrier material can include fillers, colorants, etc. that donot substantially interact with or interact with the change the functionor chemical characteristics of the gas-barrier material. In anotherexample, the gas-barrier material can consist essentially of athermoplastic ethylene-vinyl alcohol copolymer, which means that thegas-barrier material does not include a sufficient amount of anothertype of thermoplastic polymer or copolymer to alter the properties(e.g., melting temperature, melt flow index, creep relaxationtemperature, or the like) of the gas-barrier material. Further in thisaspect, when the gas-barrier material consists essentially of onepolymer type (e.g., a thermoplastic ethylene-vinyl alcohol copolymer),it may contain less than 1 weight percent of another type of polymer.

As used herein, “polyurethane” refers to a copolymer (includingoligomers) that contains a urethane group (—N(C═O)O—). Thesepolyurethanes can contain additional groups such as ester, ether, urea,allophanate, biuret, carbodiimide, oxazolidinyl, isocynaurate,uretdione, carbonate, and the like, in addition to urethane groups. Inan aspect, one or more of the polyurethanes can be produced bypolymerizing one or more isocyanates with one or more polyols to producecopolymer chains having (—N(C═O)O—) linkages.

As used herein, the terms “at least one” and “one or more of” an elementare used interchangeably, and have the same meaning that includes asingle element and a plurality of the elements, and can also berepresented by the suffix “(s)” at the end of the element. For example,“at least one polyurethane,” “one or more polyurethanes,” and“polyurethane(s)” can be used interchangeably and have the same meaning.

As used herein, a “sheet” or “film” refers to a flexible stripcomprising one or more polymeric materials, the sheet or film having athickness that is much smaller than its length and/or width. As usedherein, a “core layer” may refer to an internal layer of material in amulti-layer sheet or film. Similarly, as used herein, a “core region”may refer to one or more layers which is, or which together form, aninternal region of material in a multi-layer sheet or film. As usedherein, a “cap layer” may refer to an externally-facing layer ofmaterial in a multi-layer sheet or film. Also as used herein, a“structural layer” may refer to a layer of material in a multi-layersheet or film that is disposed between a cap layer and a core layer. Asused herein, a “tie layer” may also refer to an internal layer in amulti-layer sheet or film; wherein, typically, a tie layer comprises amaterial which increases a bond strength of the adjacent layers.

When an element or layer is referred to as being “on,” “engaged to,”“connected to,” “attached to,” or “coupled to” another element or layer,it may be directly on, engaged, connected, attached, or coupled to theother element or layer, or intervening elements or layers may bepresent. In contrast, when an element is referred to as being “directlyon,” “directly engaged to,” “directly connected to,” “directly attachedto,” or “directly coupled to” another element or layer, there may be nointervening elements or layers present. Other words used to describe therelationship between elements should be interpreted in a like fashion(e.g., “between” versus “directly between,” “adjacent” versus “directlyadjacent,” etc.). As used herein, the term “and/or” includes any and allcombinations of one or more of the associated listed items.

The terms first, second, third, etc. may be used herein to describevarious elements, components, regions, layers and/or sections. Theseelements, components, regions, layers and/or sections should not belimited by these terms. These terms may be only used to distinguish oneelement, component, region, layer, or section from another region,layer, or section. Terms such as “first,” “second,” and other numericalterms do not imply a sequence or order unless clearly indicated by thecontext. Thus, a first element, component, region, layer, or sectiondiscussed below could be termed a second element, component, region,layer, or section without departing from the teachings of the exampleconfigurations.

As used herein, the terms “crack,” “cracking,” “craze,” “crazing,”“break,” and “breakage” may be used interchangeably, to describe afracture in the gas-barrier material forming one or more gas-barrierlayers in a core region of a multi-layered film. As described below, thedegree or level of cracking can be classified as being “severecracking,” “mild cracking” or “little to no cracking,” based on theextent of the fracture within the core region and the effects thecracking has on the properties (including gas transmission rate andclarity) of a multi-layered film.

“Little to no cracking” may describe a level of cracking in which nocracking is present in the gas-barrier core, or in which a singlefracture in the gas-barrier material of a gas-barrier layer of the coremay extend within or across only a single gas-barrier layer, or only afew gas-barrier layers (and the elastomer layers directly adjacent tothem). For example, the extent of an individual fracture can bedetermined by viewing a magnified cross-section of the thickness of thecore region of the film. When observed in this manner, typically eitherno cracking in the gas-barrier layers is observed, or fractures whichaffect less than 20 percent of the gas-barrier layers, or fractureswhich affect less than 20 percent of the cross-sectional thickness ofthe core region, are observed. Typically, the edges of any fractureswhich are present do not pull away from each other and create a gap inthe core region. FIG. 9C shows micrographs of two cross-sectionalthicknesses of core regions of a multi-layer film, both of which exhibitlittle to no cracking. A multi-layer film exhibiting little to nocracking typically does not have any cracking or crazing which isvisible to the naked eye, and has an acceptably low rate of gastransmission.

“Mild cracking” may describe a level of cracking in which a singlefracture in the gas-barrier may extend across a few gas-barrier layersor across several gas-barrier layers (and the elastomer layers directlyadjacent to them), but which does not extend across a majority of the ofgas-barrier layers and elastomer layers present in the core region, orwhich does not extend across a majority of the total thickness of thecore region. For example, the extent of an individual fracture can bedetermined by viewing a magnified cross-section of the thickness of thecore region of the film. When observed in this manner, typicallyfractures which effect 3-10 gas-barrier layers, or fractures whicheffect less than 50 percent of the gas-barrier layers, or fractureswhich effect less than 50 percent of the cross-sectional thickness ofthe core region, are observed. While the edges of some fractures maypull away from each other and create a small gap in the core region,this does not occur in the majority of the fractures. FIG. 9B showsmicrographs of two cross-sectional thicknesses of core regions of amulti-layer film, both of which exhibit mild cracking. A multi-layerfilm exhibiting mild cracking may exhibit a small decrease intransparency, as the presence of mild cracks may make the film appearsomewhat hazy. In some examples, a few of the mild cracks may be visibleto the naked eye.

“Severe cracking” may describe a level of cracking in which a singlefracture in the gas-barrier layers of the core may extend across amajority of the gas-barrier layers and elastomer layers present in thecore region, or across a majority of the thickness of the core region.For example, the extent of an individual fracture can be determined byviewing a magnified cross-section of the thickness of the core region ofthe multi-layer film. When observed in this manner, a fracture mayextend across at least 50 percent of a cross-sectional thickness of thecore region, or across more than 75 percent of the cross-sectionalthickness of the core region, or across the entire cross-sectionalthickness of the core region. Often, the edges of fractures pull awayfrom each other and create a gap in the core region. FIG. 9A showsmicrographs of two cross-sectional thicknesses of core regions of amulti-layer film, both of which exhibit severe cracking. A multi-layerfilm exhibiting severe cracking typically will exhibit an unacceptablyhigh rate of gas diffusion, has a decreased level of transparency ascompared to its initial level of transparency, and includes cracks andcrazes which are visible to the naked eye.

EXAMPLES

The present disclosure is more particularly described in the followingexamples that are intended as illustrations only, since numerousmodifications and variations within the scope of the present disclosurewill be apparent to those skilled in the art.

Example 1. Multi-layer Control and Test Films were prepared and formedinto Control and Test Bladders. These Bladders were subjected torepeated flexing and releasing cycles to simulate the conditions towhich bladders are exposed to during wear when used as cushioningelements in a midsole of an article of footwear.

The Control and Test Films were all extruded films and all included agas-barrier core region formed by extruding a gas-barrier material andan elastomeric material in alternating layers. The same gas-barriermaterial (including ethylene-vinyl alcohol) and the same elastomericmaterial (including thermoplastic polyurethane) were used in the Controland Test Films. Each Film also included a structural layer positioned oneither side of the core region (2 structural layers total), and a caplayer on each film surface (2 cap layers total). The structural layersof the Control and Test Films were formed of the same materials as eachother (including thermoplastic polyurethane). The cap layers of theControl and Test Films were also formed of the same materials as eachother (including thermoplastic polyurethane).

The Bladders were prepared by thermoforming two films of the same type(i.e., 2 Control Films for the Control Bladder, 2 Test Films for a TestBladder), bonding the two films to each other to form the perimeter ofthe bladder, and filling the bladder with nitrogen gas, to form a sealedbladder containing the nitrogen gas at a pressure of about 138Kilopascals.

The sealed Control and Test Bladders were then each subjected to anumber of KIM test cycles. Following about 350,000 (350 k) to about400,000 (400 k) KIM test cycles, the appearance of the Films of theBladders was assessed by the naked eye and assigned a Cracking Level(Severe, Mild, or Little-to-No cracking). Samples of the core regions ofareas of the Films exhibiting cracking visible to the naked eye weretaken and inspected microscopically. When Little-to-No cracking wasvisible to the naked eye, the regions of the Test Bladders selected formicroscopy corresponded to the same areas where extensive cracking wasobserved in the Control Bladders.

The Control Films each included a gas-barrier core region including 32gas-barrier layers and 32 elastomeric layers, with each gas-barrierlayer directly adjacent to an elastomeric layer in an alternatingpattern. In the Control Film, the thickness of the individualgas-barrier layers ranged from about 1.0 micrometers to about 1.2micrometers. Each of the two Control Films individually had a totalthickness of about 25.4-30.8 micrometers. Following about 350,000 KIMcycles, the Control Films of the Control Bladder exhibited Severeracking. FIG. 9A shows micrographs of cross-sections of core regions ofareas of the Control Film exhibiting cracking visible to the naked eye,taken from the Control Bladder after about 350 k KIM cycles.

The First Test Films each included a gas-barrier core region including32 gas-barrier layers and 32 elastomeric layers with each gas-barrierlayer directly adjacent to an elastomeric layer in an alternatingpattern. In the First Test Film, the thickness of the individualgas-barrier layers were about 75 percent as thick as the individualgas-barrier layers in the Control Film, and so ranged from about 0.8micrometers to about 0.9 micrometers. Following about 400 k KIM cycles,the First Test Films of the First Test Bladder exhibited Mild crackingbased on visual inspection by the naked eye and microscopy. FIG. 9Bshows micrographs of cross-sections of core regions of areas of theFirst Test Film exhibiting mild cracking visible to the naked eye, takenfrom the First Test Bladder after about 400 k KIM cycles.

The Second Test Films each included a gas-barrier core region including32 gas-barrier layers and 32 elastomeric layers in the same alternatingpattern as described above. In the Second Test Film, the thickness ofthe individual gas-barrier layers were about 50 percent as thick as theindividual gas-barrier layers in the Control Film, and so ranged fromabout 0.5 micrometers to about 0.6 micrometers. Following about 400 kKIM cycles, the Second Test Films of the Second Test Bladder exhibitedLittle-to-No cracking, based on visual inspection using the naked eye aswell as microscopy. FIG. 9C shows micrographs of cross-sections of coreregions of areas of the First Test Film exhibiting mild cracking visibleto the naked eye, taken from the Second Test Bladder after about 400 kKIM cycles.

Example 2. Multi-layer Control and Test Films were prepared and formedinto Control and Test Bladders as described in Example 1. These Bladderswere subjected to repeated flexing and releasing cycles to simulate theconditions to which bladders are exposed to during wear when used ascushioning elements in a midsole of an article of footwear. The sealedControl and Test Bladders were each subjected to a total of 400,000 (400k) KIM test cycles. Before the KIM testing and following 60,000 (60 k),120,000 (120 k), and/or 320,000 (320 k) KIM test cycles, the gastransmission rate was measured for each of the Bladders (see FIGS. 10A,11A, and 12 for the exact number of cycles after which the gastransmission rate of the Control and Test Bladders were measured). Gastransmission rates (GTR) were measured in cubic centimeters per squaremeter per day. The measured gas transmission rates were used to developa gas transmission rate fatigue model using the following equation:

G=G _(m)−(G _(m) −G ₀)(1−e ^((−kx)))

where G is gas transmission rate, G₀ is the gas transmission rate priorto any KIM cycling, G_(m) is the gas transmission rate after 320,000 KIMcycles, and k is a growth parameter depending on gas-barrier layerthickness as well as the type and number of gas-barrier layers in thefilms of the bladder. Following 400,000 (400 k) KIM test cycles, theappearance of the Films of the Bladders was assessed as described inExample 1.

Example 2A. The Control Films and Control Bladder, as well as the SecondTest Films and Second Test Bladders used in Example 2A were the same asin Example 1. The Third Test Films each included a gas-barrier coreregion including 24 gas-barrier layers alternating with 24 elastomericlayers, 33 percent fewer gas-barrier layers than in the Control andSecond Test Films. In the Third Test Film, the thickness of individualgas-barrier layers was about 50 percent of individual gas-barrier layersin the Control Film, and so ranged from about 0.5 micrometers to about0.6 micrometers.

FIG. 10A shows the GTRs measured for the Control Bladder (bottom curve)and for the Second Test Bladder (middle curve), and for the Third TestBladder (top curve) after the indicated number of KIM cycles. FIG. 10Aalso shows the GTR calculated using the above equation for 240,000 KIMcycles (GTR_(240k)). Unexpectedly, the measured and calculated GTRs forboth the Second and Third Test Bladders were all only slightly higherthan for the Control Bladder and were still comfortably below thedesired maximum of 3 cubic centimeters per square meter per day. Thiswas unexpected as the gas-barrier layers of both the Second and ThirdTest films were 50 percent thinner than those of the Control Film, andthe Third Test Film contained 33 percent fewer of these thinnergas-barrier layers than the Second and Control Test Films.

As in Example 1, following 400 k KIM cycles, areas of the Control Filmsof the Control Bladder exhibited Severe cracking, while areas of theSecond Test Films of the Second Test Bladder exhibited Little-to-Nocracking. The Third Test Films of the Third Test Bladder also exhibitedLittle-to-No cracking. FIG. 10B shows micrographs of cross-sections ofcore regions of areas of the Second Test Film. FIG. 10C showsmicrographs of cross-sections of core regions of areas of the Third TestFilm exhibiting Little-to-No cracking.

Example 2B. The Control Films and Control Bladder, as well as the FirstTest Films and First Test Bladders used in Example 2B were the same asin Example 1. The Third Test Films and the Third Test Bladder were thesame as in Example 2A.

FIG. 11A shows the GTRs measured for the Control Bladder (bottom curve)and for the First Test Bladder (middle curve), and for the Third TestBladder (top curve) after the indicated number of KIM cycles. FIG. 11Aalso shows the GTR calculated as in Example 2A. As in Example 2A,unexpectedly, the measured and calculated GTRs for both the First andThird Test Bladders were all only slightly higher than for the ControlBladder and were still comfortably below the desired maximum of 3 cubiccentimeters per square meter per day. The calculated GTR for the FirstTest Bladder (2.10 cc/m²·day) was only slightly lower than the GTRcalculated for the Second Test Bladder (2.15 cc/m²·day). This wasunexpected as the gas-barrier layers of the Second Test Film were abouta third thinner than the First Test Film (the thickness of thegas-barrier layers in the Second Test Film were about 50 percent of thethickness as the gas-barrier layers in the Control Film, while thethickness of the gas-barrier layers in the First Test Film were about 75percent of the thickness of the gas-barrier layers in the Control Film).

As in Examples 1 and 2A, following 400 k KIM cycles, areas of theControl Films of the Control Bladder exhibited Severe cracking, whileareas of the First Test Films of the First Test Bladder exhibited Mildcracking, and the Third Test Films of the Third Test Bladder exhibitedLittle-to-No cracking. FIG. 11B shows micrographs of cross-sections ofcore regions of areas of the First Test Film.

Example 2C. The Control Films and Control Bladder used in Example 2Cwere the same as in Example 1. The Fourth Test Films each included agas-barrier core region including 40 gas-barrier layers alternating with40 elastomeric layers as described above. The Fourth Test Films included25 percent more gas-barrier layers than in the Control Films. In theFourth Test Films, the thickness of the individual gas-barrier layerswas the same as in the Control Films, and so ranged from about 1.0micrometers to about 1.2 micrometers. The Fifth Test Films each includeda gas-barrier core region including 60 gas-barrier layers alternatingwith 60 elastomeric layers as above. The Fifth Test Films included over87 percent more gas-barrier layers than in the Control Films. In theFifth Test Films, the thickness of the individual gas-barrier layers was150 percent of their thickness in the Control Films, and so ranged fromabout 1.5 micrometers to about 1.8 micrometers.

FIG. 12 shows the GTRs measured for the Fourth Test Bladder (top curve),and for the Fifth Test Bladder (bottom curve) after the indicated numberof KIM cycles. FIG. 11A also shows the GTR calculated as in Examples 2Aand 2B. The measured and calculated GTRs for the Fifth Test Bladder waslower than for the Control Bladder other Test Bladders, as would beexpected based on the increased thickness and number of the gas-barrierlayers. The measured and calculated GTR (2.24 cubic centimeters persquare meter per day) for the Fourth Test Bladder were higher than forthe Fifth Test Bladder, but surprisingly were also higher than for theFirst and Second Test Bladders (calculated GTR of 2.10 cubic centimetersper square meter per day and 2.15 cubic centimeters per square meter perday, respectively). This was unexpected as the First and Second TestFilms each had thinner gas-barrier layers and fewer gas-barrier layersthan the Fourth Test Film.

As in Examples 1, 2A and 2B, following 400 k KIM cycles, areas of theControl Films of the Control Bladder exhibited Severe cracking, whileareas of the Fourth Test Films of the Fourth Test Bladder and of theFifth Test Films of the Fifth Test Bladder both exhibited Mild cracking.

The results of Examples 1 to 2C are summarized in Table 1.

Overall Cracking Level Total Thickness of Observed Number Individual forFilm of Gas- Gas-Barrier after Barrier Layers in ~400 k KIM Example 1Bladder Layers micrometers cycles Control 32 1.0-1.2 Severe BladderCracking 1^(st) Test 32 0.8-0.9 Mild Bladder Cracking 2^(nd) Test 320.5-0.6 Little to No Bladder Cracking Overall Calculated Cracking GasLevel Transmission Total Thickness of Observed Rate (GTR) NumberIndividual for Film for Test of Gas- Gas-Barrier after Bladder BarrierLayers in ~400 k KIM at 240 k Example 2A Bladder Layers micrometerscycles KIM cycles Control 32 1.0-1.2 Severe Bladder Cracking 2^(nd) Test32 0.5-0.6 Little to No 2.15 Bladder Cracking 3^(rd) Test 24 0.5-0.6Little to No 2.70 Bladder Cracking Overall Cracking Level CalculatedTotal Thickness of Observed GTR Number Individual for Film for Test ofGas- Gas-Barrier after Bladder Barrier Layers in ~400 k KIM at 240 kExample 2B Bladder Layers micrometers cycles KIM cycles Control 321.0-1.2 Severe Bladder Cracking 1^(st) Test 32 0.8-0.9 Mild 2.10 BladderCracking 3^(rd) Test 24 0.5-0.6 Little to No 2.70 Bladder CrackingOverall Cracking Level Calculated Total Thickness of Observed GTR NumberIndividual for Film for Test of Gas- Gas-Barrier after Bladder BarrierLayers in ~400 k KIM at 240 k Example 2C Bladder Layers micrometerscycles KIM cycles Control 32 1.0-1.2 Severe Bladder Cracking 4^(th) Test40 1.0-1.2 Mild 2.24 Bladder Cracking 5 ^(th) Test 60 1.5-1.8 Mild 1.28Bladder Cracking

As a person skilled in the art will readily appreciate, the abovedescription is meant as an illustration of the implementation of theprinciples of this invention. This description is not intended to limitthe scope or application of this invention in that the invention issusceptible to modification, variation, and change, without departingfrom the spirit of this invention as defined in the following claims.

What is claimed is:
 1. A cushioning element comprising: a multi-layeredfilm including one or more core regions, each core region comprising aplurality of gas-barrier layers comprising at least one gas-barriermaterial and a plurality of elastomeric layers comprising at least oneelastomeric material, wherein the gas-barrier layers alternate with theelastomeric layers, wherein each of the gas-barrier layers comprises atleast one gas-barrier material and has an average thickness in a rangeof from about 0.01 micrometers to about 0.75 micrometers, and whereineach of the plurality of elastomeric layers comprises at least oneelastomeric material and has an average thickness ranging from about 2micrometers to about 8 micrometers.
 2. The cushioning element of claim1, wherein the plurality of gas-barrier layers of the multi-layered filmcomprises at least 20 gas-barrier layers.
 3. The cushioning element ofclaim 1, wherein the at least one gas-barrier material comprises anitrogen barrier material.
 4. The cushioning element of claim 3, whereinthe at least one gas-barrier material comprises or consists essentiallyof one or more gas-barrier polymers, and wherein the at least onegas-barrier material comprises a gas-barrier polymeric componentconsisting of all polymers present in the at least one gas-barriermaterial.
 5. The cushioning element of claim 4, wherein the one or moregas-barrier polymers comprise or consist essentially of one or morethermoplastic vinylidene chloride polymers, one or more thermoplasticacrylonitrile polymers or copolymers, one or more thermoplasticpolyamides, one or more thermoplastic epoxy resins, one or morethermoplastic amine polymers or copolymers, or one or more thermoplasticpolyolefin homopolymers or copolymers.
 6. The cushioning element ofclaim 5, wherein the one or more thermoplastic polyolefin homopolymersor copolymers comprise or consist essentially of one or morethermoplastic ethylene-vinyl alcohol copolymers.
 7. The cushioningelement of claim 6, wherein the one or more thermoplastic ethylene-vinylalcohol copolymers include from about 28 mole percent to about 44 molepercent ethylene content.
 8. The cushioning element of claim 1, whereinthe at least one elastomeric material comprises or consists essentiallyof one or more thermoplastic elastomeric polymers, and wherein the atleast one elastomeric material comprises an elastomeric polymericcomponent consisting of all polymers present in the elastomericmaterial.
 9. The cushioning element of claim 8, wherein the one or morethermoplastic elastomeric polymers comprise or consist essentially ofone or more thermoplastic elastomeric polyolefin homopolymers orcopolymers, one or more thermoplastic elastomeric polyamide homopolymersor copolymers, one or more thermoplastic elastomeric polyesterhomopolymers or copolymers, one or more thermoplastic elastomericpolyurethane homopolymers or copolymers, one or more thermoplasticelastomeric styrenic homopolymers or copolymers, or any combinationthereof.
 10. The cushioning element of claim 9, wherein the at least oneelastomeric material comprises or consists essentially of one or morethermoplastic elastomeric polyurethane homopolymers or copolymers. 11.The cushioning element of claim 1, further comprising a recycledmaterial comprising one or more recycled polymers, optionally whereinthe recycled material comprises one or more recycled thermoplasticelastomers.
 12. The cushioning element of claim 1, further comprisingone or more tie layers, each of the one or more tie layers individuallycomprising or consisting essentially of a tie material, wherein the oneor more tie layers increase a bond strength between two adjacent layers.13. The cushioning element of claim 12, wherein the tie material of eachof the one or more tie layers independently comprises or consistsessentially of a polyurethane, a polyacrylate, an ethylene-acrylatecopolymer, a maleic anhydride grafted polyolefin, or any combinationthereof.
 14. The cushioning element of claim 1, further comprising oneor more structural layers, each of the one or more structural layersindependently comprising or consisting essentially of a structural layermaterial.
 15. The cushioning element of claim 14, wherein the structurallayer material of each of the one or more structural layersindependently comprises or consists essentially of a polydienepolyol-based thermoplastic polyurethane.
 16. The cushioning element ofclaim 1, further comprising one or more cap layers, wherein the one ormore cap layers comprise or consist essentially of a cap layer material.17. The cushioning element of claim 16, wherein the cap layer materialof the one or more cap layers comprises or consists essentially of apolyurethane, a polyacrylate, an ethylene-acrylate copolymer, a maleicanhydride grafted polyolefin, or any combination thereof.
 18. Thecushioning element of claim 1, wherein each of the one or more coreregions has a gas transmission rate of from about 0.3 to about 1.9 cubiccentimeters per square meter per day for nitrogen measured at 23 degreesCelsius and 0 percent relative humidity for a structure having athickness of from about 72 micrometers to about 320 micrometers.
 19. Anarticle comprising the cushioning element of claim
 1. 20. The article ofclaim 19, wherein the article comprises an article of footwear, acomponent of an article footwear, an article of apparel, a component ofan article of apparel, an article of sporting equipment, a component ofan article of sporting equipment, a personal protective article, aflexible flotation device, a rigid flotation device, a medical device, aprosthetic device, an orthopedic device, an accumulator, an article offurniture, or a component of an article of furniture, a tire, or a hose.